Annual report 2013 institute acqua on mineral resources, water and biodiversity (1) by Atelier Online

summary 4 introduction 10 facts and figures 12 national and international partnerships 20 educational and outreach activities 26 science highlights 28 assessment of water/environmental quality and aquatic biodiversity

60 modeling and simulation of

hydrometallurgical processes

76 natural and synthetic materials for

environmental and technological applications

86 acid rock drainage 94 publications 98 contacts

introduction

“Calçada” mountain range, Minas Gerais, Brazil. Ilana Lanky, 1st award winner of the photograph contest sponsored by “Geopark Quadrilátero Ferrífero”.

National Institute of Science and Technology on Mineral Resources, Water and Biodiversity – INCT-ACQUA Instituto Nacional de Ciência e Tecnologia em Recursos Minerais, Água e Biodiversidade

Foreword A program launched by the Brazilian Ministry of Science, Technology and Innovation (MCTI) established the National Institute of Science and Technology on Minerals Resources, Water and Biodiversity – INCT-Acqua, in 2009. By combining and integrating Mineral Resources, Water and Biodiversity, the INCT-Acqua adopts a new paradigm, where water is the common denominator of the initiatives focused on innovation, scientific development, social and sustainable regional development. The activities of the Institute encompasses two major areas: (i) the assessment of the impact of mining activities on the quality of water, soil, air and conservation of biodiversity; and (ii) adding value and environmental performance to mineral-based products and processes. The following scientific, conceptual and restoration achievements are worth to be highlighted. The onset of criteria, methodologies, and mechanisms to restore c. 40 km stretch of the São Francisco river disclosed new perspectives for the restoration of contaminated sediments in large rivers in Brazil. Ecotoxicity assays using native species provided significant and innovative methodological and technological improvements. Analytical tools were adapted and applied for a comprehensive and solid understanding of potential risks related to the availability and mobility of toxic trace elements from a gold mine site. Concerning processes and products, it is worth notice the development of processes (patents submitted) for cyanide recovery as well as the conducting of promising tests for bioaccumulation of arsenic using cyanobacteria. The investigation of the role of impurities on zinc electrowinning will contribute to the development of best practices and the reduction of energy consumption in the industrial processes. Magnetic nanocomposites and functionalized clay materials were developed and applied for decomposition and removal and immobilization of inorganic and organic contaminants. Mine sites that generate acid rock drainage were investigated in detail and processes to treat acid water and to remove contaminants were well established. The use of slag from steel production and floating macrophytes were shown to be promising, alternative methods for remediation of these sites. The combining of theoretical molecular modeling and measurements using synchrotron radiation and other techniques allowed for a significant advance on the understanding of reactions participating in the processes of extracting metals (e.g. from copper sulfide and from gold-copper ores), fixing contaminants (cyanide, arsenic and dyes), and biological speciation of arsenic using cyanobacteria. Furthermore, biodiversity assessment in mining areas reinforce the need of conservation of water quality and biodiversity in these areas, including the mining sector among the ones providing effective support to conservation actions. The interaction with the industrial sector, which is not trivial, was built on effective collaboration with anchor companies such as Kinross, Votorantim Metais, and INB/CNEN in research projects of comprehensive thematic scope and strong transdisciplinary and multi-institutional characteristics. The AMIRA project itself joins eleven (11) companies providing funds in a consortium mode to five (5) research groups from Canada, United States, Australia, and Brazil collaborating on research themes in a pre-competitive stage. The above models help to promote investigations in frontier areas, with direct benefits for the industrial sector and significant gains in capacity building. The expressive volume of resources from the private sector attests not only to the recognition of the INCT-Acqua team, but also to the relevance of the activities performed within the Institute. Other actions aiming at complementary fund raising in thematic areas of the Institute have resulted in the signing of the FAPEMIG–QUEENSLAND agreement bringing US$2 million in financial support for research projects, in addition to US$1 million (FAPEMIG) for the installation of a laboratory for advanced mineral characterization (the first of its kind in Minas Gerais) in the Centre for Microscopy at the Federal University of Minas Gerais (UFMG). Collaboration with public sectors has been even further expanded through strategic partnerships with the Iron Quadrangle Geopark and the Mineral and Metallurgical Pole of Excellence. This partnership has incorporated an entire network and group of national and international relations within the Institute. A remarkable outcome was the creation of the Center of Reference and Qualification for the Sustainability of the Alto Paraopeba Region (CESUP), based in Conselheiro Lafayette, as a result of a formal cooperation

INTRODUCTION |

instrument with CODAP – Public Consortium for The Development of the Alto Paraopeba. By facilitating interactions with the local community and the transfer of knowledge, this outpost shall contribute to the formulation of public policies on development and sustainability for the region. Graduate programs dealing with projects with companies (e.g. Votorantim Metais, Kinross, and Vale) and overseas collaborations, for example, through multi-institutional PhD programs, are also noteworthy. Visiting researchers offered a wide range of courses and cooperated with Brazilian researchers. Lectures and workshops were offered for elementary public school teachers and supplementary didactic-pedagogical materials were distributed. Furthermore, in partnership with BHTrans, the project, “Travelling with the Environment”, has produced four (4) scientific texts launched on specific bus lines in the city of Belo Horizonte. A public of nearly 5,000 people had access to the texts. A specially designed bus “Aquamundo” has been travelling across the country-side of São Paulo and Minas Gerais states, offering interactive images on water issues and water biodiversity to the general public, schoolchildren, and schoolteachers. It is also important to note the widespread connection with the international community, with several visitors from companies and universities, as well as technical missions abroad. Over the 48 months that followed the creation of INCT-Acqua, the organization has matured greatly as regards its central question: “How to conciliate industrial growth with the conservation of water resources, biodiversity, and cultural heritage?” This process culminated in the organization of the Building the Future Forum, held in August 2011, which laid the foundation for a new phase in INCT-Acqua’s work, focusing on iron ore mining in the Iron Quadrangle (IQ) as a target of pilot and demonstrative projects. The scientific, technological, and strategic content of innovation to be incorporated within this pioneering initiative of INCT-Acqua shall have a very positive impact upon the IQ region and become a model to be replicated in other areas. The creation of the Advisory Board, at that time, established a permanent external assessment, aimed at contributing towards forefront research and the longevity of the Institute. All of the actions developed over these four years have allowed the INCT-Acqua to tackle broad scale and complex issues, which underpins the proposed theme of the Institute, as well as to render the excellent results detailed in the present report. Virginia Ciminelli, Francisco Barbosa and José Galizia Tundisi June 2013

Premises Mineral resources, water and biodiversity are competitive advantages and should guide initiatives focused on capacity building, innovation, and scientific, economic and social development.

Water is a transformation agent to promote innovation, to increase industrial competitiveness, social approval and a regional sustainable development.

Scope Provide a comprehensive evaluation of the environmental impact of the mineral industry on water, sediments, air and on aquatic biodiversity. Re-design industrial processes with the aim of minimizing the consumption of natural resources and the production of wastes. Develop innovative and integrative approaches for the diagnosis and remediation of impacted mining areas. Focus on capacity building, with new perspectives of sustainability and business diversity. Assist stakeholders in shaping the future of mining territories.

6 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

MANAGEMENT COMMITTEE Virginia Sampaio T. Ciminelli – UFMG, Director José Galizia Tundisi – IIEGA-SP, Vice-Director Francisco Antônio Rodrigues Barbosa – UFMG, Vice-Director Ângela de Mello Ferreira – CEFET/MG Ana Claudia Queiroz Ladeira – CNEN/ CDTN Jaime Wilson Vargas de Mello – UFV Hélio Anderson Duarte – UFMG ADVISORY COUNCIL Renato Ciminelli (President) – The Mineral and Metallurgic Pole of Excellence – President, Geopark Iron Quadrangle Evando Mirra de Paula e Silva – Emeritus Professor, UFMG Carlos Nogueira Costa Júnior – Secretary of Geology, Mining and Mineral Processing, MME Francisco Alves – Editorial Director, Brasil Mineral Magazine Silvio Crestana – Researcher and Former President of Embrapa Leonardo Santana Dias – Geotechnical Manager, COFFEY Mining LEADING INSTITUTIONS Universidade Federal de Minas Gerais – UFMG Instituto Internacional de Ecologia e Gerenciamento Ambiental – IIEGA Universidade Federal de Viçosa – UFV Centro de Desenvolvimento da Tecnologia Nuclear – CNEN/CDTN Centro Federal de Educação Tecnológica de Minas Gerais – CEFET/MG NATIONAL COLLABORATION Universidade Federal do Ceará – UFCe Universidade Federal de Juiz de Fora – UFJF Universidade Federal de São João Del Rei – UFSJ Universidade Federal dos Vales do Jequitinhonha e Mucuri – UFVJM PROGRAMS AND PROJECTS ON TERRITORIAL DEVELOPMENT Mineral and Metallurgic Pole of Excellence – Secretaria de Estado de Ciência, Tecnologia e Ensino Superior de Minas Gerais – SECTES Geopark Iron Quadrangle Public Consortium for the Alto Paraopeba Development – CODAP Technological Park Alto Paraopeba COLLABORATION IN SPECIFIC PROJECTS COFFEY Information EIP – Espaço Israel Pinheiro GOLDER Associates IGAM – Instituto Mineiro de Gestão das Águas INB – Indústrias Nucleares do Brasil KINROSS LAPOC – Laboratório Poços de Caldas OSCIP Verde Novo PETROBRÁS SANAP – South America Network of Acid Mine Drainage VALE – DIDN – Gerência de Meio Ambiente VM – Votorantim Metais INTERNATIONAL COLLABORATION Centro Atômico Constituintes, Comisión Nacional de Energia Atómica – Argentina Karlsruhe Institute of Technology – Germany Jacobs University – Germany Murdoch University – Australia Ohio University – United States of America The Pennsylvania State University – United States of America University of Guelph – Canada University of Queensland – Australia

INTRODUCTION |

• Karlsruhe Institute of Technology (Germany) • Jacobs University (Germany) • University of Guelph (Canadá) • The Pennsylvania State University (EUA) • Ohio University (EUA)

• Universidade Federal do Ceará (UFCe) • EIP – Espaço Israel Pinheiro (GO)

• INCT-ACQUA • Indústrias Nucleares do Brasil (INB)

• Universidade Federal de Minas Gerais – UFMG • Universidade Federal de Viçosa – UFV • Centro de Desenvolvimento da Tecnologia Nuclear – CDTN

• Instituto Internacional de Ecologia e Gerenciamento Ambiental (IIEGA)

• Centro Federal de Educação Tecnológica de Minas Gerais – CEFET/MG • Universidade Federal do Ceará – UFCe • Universidade Federal de Juiz de Fora – UFJF • Universidade Federal de São João Del Rei – UFSJ • Universidade Federal dos Vales do Jequitinhonha e Mucuri - UFVJM • Mineral and Metallurgic Pole of Excellence – Secretaria de Estado de Ciência, Tecnologia e Ensino Superior de Minas Gerais – SECTES • Geopark Iron Quadrangle • Public Consortium for the Alto Paraopeba Development – CODAP • Technological Park Alto Paraopeba • COFFEY Information • EIP – Espaço Israel Pinheiro • IGAM – Instituto Mineiro de Gestão das Águas • OSCIP Verde Novo • LAPOC – Laboratório de Poços de Caldas • GOLDER Associates • KINROSS - Paracatu • PETROBRAS • VM – Votorantim Metais • VALE – DIDN – Gerência de Meio Ambiente

• Centro Atômico Constituintes, Comisión Nacional de Energia Atómica (Argentina)

• University of Queensland (Australia) • Murdoch University (Australia)

INCT-ACQUA Network

facts and figures

Research Indicators: Publications Books Book Chapters Journals Proceedings Books

Knowledge and Technology Transfer Indicators

8 11 78 68

57 Events in Communities, Elementary and Secondary Schools 2 Patent Deposits 19 Projects with Industries and Others 6 Interaction with Other Projects

Education and Outreach Activities Indicators 12

Educational Materials

2 2

Capacity Building â&#x20AC;&#x201C; Graduate and Post-Graduate Courses

Printed Media, Digital Games and Installations

Short Courses

Videos

7 2

Awards

Website, Catalogs of INCT-Acqua, Folders, Portfolio Briefcase and Annual Report

Newsletter

Invited Lectures

22 5

Research Exchange and Missions

Events

Seminars News for Radio Broadcast, TV, Magazines and websites

Capacity Building Indicators Current Undergraduate Students M.Sc and PhD Students Post-Doctorates Technical Level

19 17 9 14

Concluded 22 19 13 17

FACTS AND FIGURES |

national and international partnerships

The INCT-Acqua hosted many visitors, from foreign companies and universities. Visiting professors offered seminars, short-courses and interacted with the Brazilian researchers. Collaboration with the public sector - the Mineral and Metallurgical Pole of Excellence/SECTES-MG - culminated with the creation of the Center of Reference and Qualification for the Sustainability of the Alto Paraopeba Region - CESUP, which shall contribute to the formulation of public policies on development and sustainability. The expressive volume of resources from the private sector attests not only to the recognition of the INCT-Acqua team, but also to the relevance of the activities performed within the Institute.

Events 2nd Preparatory Meeting for the World Science Forum 2013 – “Science for Global Development” – Challenges for scientific and technological development in the tropics. Round Table: Science, Technology and Innovation for preservation and management of Water Resources. UFMG, Belo Horizonte, Brazil. October, 29-30, 2012. Virginia S. T. Ciminelli – Organizing committee and session co-chair Francisco A. R. Barbosa – Rapporteur

XVI Brazilian Symposium on Theoretical Chemistry – SBQT. Ouro Preto – MG, Brazil. November, 20-24, 2011. Hélio A. Duarte – Organizer

Forum INCT-Acqua: Building the Future. Panel 1 – Academy Partnership – Company, in projects of great extension; Panel II – The New Dimensions of Mining: risks and opportunities; Round Table. II Workshop of the INCT-Acqua. School of Engineering, UFMG. Belo Horizonte, Brazil. School of Engineering, UFMG/ ABC. Belo Horizonte, Brazil. August, 30, 2011.

“Wetland Ecotechnologies for Wastewater and Stormwater Management – their ecological, social and economic benefits” School of Engineering, UFMG. June, 18, 2012. Margaret Greenway (Griffith University, Australia)

“Core Research Lines and Services at Griffith University” School of Engineering, UFMG. June, 18, 2012. Guie X Hartney (Griffith International, Australia)

“X-ray Diffraction and Rietveld Method (XRD, crystallography and mathematics basis required for quantitative analysis)” – Centro Federal de Educação Tecnológica de Minas Gerais-CEFET-MG. School of Engineering, UFMG. March, 13, 2012. Peter George Weidler (Institute for Functional Interfaces – Karlsruhe Institute of Technology, Germany)

“Reduction of Pentavalent arsenic and Trivalent for photocatalysis with TiO2” School of Engineering, UFMG. February, 28, 2012. Marta Litter (Centro Atómico Constituyentes, Comisión Nacional de Energía Atômica, Argentina)

Renato Cimnelli, Virginia Ciminelli, Francisco A. R. Barbosa,

“Contribution of Anthropogenic Heavy Metals to Potengi River Estuary, Natal, Rio Grande do Norte” School of Engineering, UFMG. February, 15, 2012.

José Galízia Tundisi – Organizers

Raquel Franco de Souza (Universidade Federal do Rio Grande do

Peter George Weidler (Institute for Functional Interfaces –

Norte, Brazil)

Karlsruhe Institute of Technology, Germany)

Workshop “Challenges for Capacity Building and Research in Water Resources in Brazil”. São Carlos- SP, Brazil. May, 30, 2011. José Galízia Tundisi – Organizer

“Challenges and Prospects for Generation Photovoltaic of Energy” CEFET-MG. November, 21, 2011. Gianluca Timó (Centro de Pesquisas Ricerca sul Sistema Energético, Itália),Alexandre Francisco Maia Bueno (CEMIG, Brazil), José Roberto Branco (CETEC, Brazil), Marcelo Franco (Secretaria de Estado de Ciência, Tecnologia e Ensino Superior de

Seminars “Speciation of arsenic, chronic hydroarsenicism regional endemic: 20 years of history in CNEA / Argentina” School of Engineering, UFMG. June, 25, 2012

Minas Gerais, Brazil).

“Solar Cells: contributions of Chemistry and Science and Materials Engineering for the Advancement of Renewable Energy” CEFET-MG. November, 20, 2011. Gianluca Timó (Centro de Pesquisas Ricerca sul Sistema

Silvia Farías (Comisión Nacional de Energía Atómica, Argentina)

Energético, Itália)

“Planning Healthy and Sustainable Cities and Communities” School of Engineering, UFMG. June, 18, 2012.

“Sedimentation in Artificial Water Systems: Risks and Proposed Remediation” School of Engineering, UFMG. May, 27, 2011.

Peter Davey (Griffith University, Australia)

Rita Fonseca (Universidade de Évora, Portugal)

NATIONAL AND INTERNATIONAL PARTNERSHIPS |

“A Global Perspective of Arsenic Risks” School of Engineering, UFMG. May, 20, 2011.

Virginia S.T. Ciminelli – UFMG, Brazil & K. Osseo-Asare

Jack Ng (University of Queensland, Australia)

Metallurgical and Materials Engineering Week. October, 2011.

Visit to Universidade Federal do Ceará – Brazil and lecture in the

Hélio A. Duarte – UFMG, Brazil

Researcher Exchange and Missions Hélio A. Duarte – UFMG, Brazil Centro de Investigacion y del Estudios Avanzados – Cinvestav. Instituto Polytechnic National – Department of Chemistry.

Jacobs University, Bremen, Germany, WE-Heraeus Summer School 2011. July, 03-15, 2011.

Hélio A. Duarte; Heitor A. Abreu; Luciana Guimarães – UFMG, Brazil Jacobs University, Bremen. Germany, XI deMon Developers

Professor Andreas Koster Group. Financial Support: CIAM-2008

Workshop. July, 01-03, 2011.

(Work mission. México) July 03-11, 2012

Virginia S.T. Ciminelli – UFMG, Brazil

Hélio A. Duarte – UFMG, Brazil

State of Minas Gerais/FAPEMIG – Foundation for the Support

University of Calgary, Alberta, Canadá. (Work mission). April,

of Research in the State of Minas Gerais – guest to the Third

11-18, 2013.

Israeli Presidential Conference Facing Tomorrow 2011, under the

Jaime W. V. de Mello – UFV, Brazil Senior Internship. School of Earth Sciences. The University of Queensland, Australia. July/2012 to March/2013.

Lívia Ribeiro de Souza – CDTN, Brazil Helmholtz Centre for Environmental Research (UFZ), in Halle, Germany. (Research mission) Stable Isotopic determinations

auspices of the President Shimon Peres – Innovation Edge 2011, Jerusalem, Israel, 19-25 June 2011.

Virginia S.T. Ciminelli; Renato Ciminelli – UFMG, SECTES, Brazil Universidade de Évora and Universidade de Lisboa, Portugal. (Seminar and Work mission). June, 14-16, 2011.

to assess the impact of mining activities on the environment.

Virginia S. T. Ciminelli; Renato Ciminelli (organizers) –

Outubro, 2012

UFMG, SECTES, Brazil

Hélio A. Duarte – UFMG, Brazil

Technical mission of the State of Minas Gerais to LILLE, France.

Jacobs University, Bremen, Germany, (Probral CAPES/DAAD).

Visit to Université de Lille, Government of Nord Pás de Calais, Pole

August 26 – Sept 05 , 2012.

cd2e, Mission Bassin Minner, France. Participation in the Environord

Daniel Majuste – UFMG, Brazil

2011.

Salt Lake City, USA – The University of Utah and FLSmidth Inc. – (Work mission). AMIRA Project P705B. June, 25-28, 2012

Renato Ciminelli – SECTES, Brazil

European Congress of Eco-Technology for the Future. June, 2-12,

Daniel Majuste – UFMG, Brazil Post-doctoral activities and participation in the Sponsors review meeting, AMIRA Project P705-B: improved anode and cathode

Mission in France, Nord Pás de Calais region, participation on the

process in base metal electrowinning. (Work mission). Murdoch

II Forum of Cooperation Actors between Minas Gerais and Nord

University, Australia May and June, 2011.

Pas de Calais. December, 05-08, 2011.

Daniel Majuste – UFMG, Brazil Project meeting AMIRA International LTD. (AMIRA Project P705-B). Santiago, Chile. November, 2011.

Ângela de Mello Ferreira – CEFET/MG, Brazil Université Joseph Fourier – Grenoble, France (work mission) Lecture -”Heavy Metal in the Environment, and waste water treatment methods” SIMAP Laboratories (Science et Ingénierie

José Galizia Tundisi – IIEGA, Brazil

des Matériaux et Procédés), March, 2011 LEPMI (Laboratoire

Meeting of Panel of Waters of Interamerican Association of

d’Electrochimie et de Physico-chimie des Matériaux et des

Academies of Sciences. Bolivia, November, 24-25, 2011.

Interfaces), April, 2011 MINATEC (Micro and Nanotechnologies

Susan Glasauer – University of Guelph – Canada Fieldwork at Kinross, UFV and meetings. Brazil, October, 2011.

Henri Dumont (University of Gent, Belgium) Meetings to discuss research projects in collaboration with Prof. Francisco A. Barbosa. Brazil, October/November, 2011.

innovation Campus) which involves researchers from Grenoble INP, CNRS (Centre National de la Recherche Scientifique) and Universite Joseph Fourier. May,2011.

Hélio A. Duarte – UFMG, Brazil Pennsylvania State University, State College – USA. (Prof. Kwadwo Oseo-Asare Group)(Work mission). February,13-17, 2011.

Massimo Gasparon (University of Queensland, Australia)

Hélio A. Duarte; Heitor A. Abreu – UFMG, Brazil.

Fieldwork at Kinross, Paracatu. Brazil, November/December,

University of Calgary, Alberta, Canadá. (Work mission). February,

2011.

07-12, 2011.

14 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

Invited Lectures (from a total of 43) 8th Workshop on Computational Chemistry and Molecular Spectroscopy. “Nanostructured Clay Minerals”. Punta de Tralca, Chile. October, 23-26, 2012 Hélio A. Duarte

Annual Seminar IEAT 2012 – “The Paths of Technological Convergence”. IEAT/UFMG, Belo Horizonte, Brazil. September, 18- 21, 2012. Evando Mirra de Paula e Silva

The 8th International Conference on the Analysis of Geological and Environmental Materials – “Geoanalytical needs to conciliate mineral production with water resources, biodiversity and cultural heritage conservation” (Plenary Lecture), Búzios, Brazil. September 20, 2012. Virginia S. T. Ciminelli

ASLO Aquatic Science Meeting 2012. “From in situ Oligotrophication experiments to N and P Loads modeling to identify restoration strategies of a hypereutrophic urban reservoir”. Lake Biwa – Shiga, Japan. July 8-13, 2012. Francisco Barbosa

Center for Research and Advanced Studies of the National Polytechnic Institute – Department of Chemistry- CINVESTAV. “Nanostructured Clay Mineral and Sulfide Mineral Reactivity – Progress report of the Brazilian Initiative INCT-ACQUA (Mineral Resources, Water and Biodiversity)”. Mexico City, Mexico. July, 04, 2012. Hélio A. Duarte

The University of Utah and FLSmidth Inc. “The effects of bornite and pyrite on the dissolution mechanism of chalcopyrite at low temperatures”. Salt Lake City, USA. June, 22 and June 25, 2012. Daniel Majuste

International Symposium Enhancing Water Management Capacity in a Changing World: Science Academies Working Together to Increase Global Access to Water and Sanitation – IAP/ InterAmerican Network of Academies of Sciences (IANAS/) Brazilian Academy of Sciences. “Mining and Water Resources: Coping with the Impacts”. São Paulo, Brazil. June, 26, 2012. Virginia S. T. Ciminelli

United Nations Conference on Sustainable Development (Rio +20) – “INCT-Acqua and the construction of a new model for the future of the miners territories”. Rio de Janeiro, Brazil. June, 20, 2012. Francisco A. R. Barbosa

VI ENQAmb – National Meeting of Environmental Chemistry 2012 – “Environmental chemistry as a tool in building models of industrial development with conservation of mineral resources, water, biodiversity and cultural patrimony”. Londrina, Brazil. March, 2012. Ana Claudia Ladeira

1st International Workshop on Computer Simulations of Thermally Excited Molecules and Materials by First Principles. “Nanostructured Clay Minerals”. Nagoya, Japan. March, 10-11, 2012. Hélio A. Duarte

Mineral Resources and Territorial Sustainability. MME/MCTI/CETEM. Round Table: The mining of large mines and the dimensions of sustainability. “The pole of mineral and metallurgical excellence of Minas Gerais”. Brasilia, Brazil, December 2011. Renato Ciminelli

International Innovation Forum: Israelis Solutions in Water for Mining, Agriculture and Industry «The view of Brazilians experts and executives and Israelis to the challenges of innovation, management, quality and water conservation». Belo Horizonte, MG. October, 24, 2011. Virginia S. T. Ciminelli

NATIONAL AND INTERNATIONAL PARTNERSHIPS |

XXIV Brazilian Meeting on Mineral Processing and Extractive Metallurgy “Aqueous Processing Research: Insights from Colloid- and Nano-Science”. Salvador, Brazil, October 16-20, 2011. K. Osseo-Asare (The Pennsylvania State University – USA)

XIII Brazilian Congress of Limnology – Round table: “The Limnology as a tool for science communication and science education”. Natal, Brazil. September, 04-09, 2011. José Galizia Tundisi

XXXIII Brazilian Congress of Soil Science. Round table. Lecture “Guiding Values for trace elements (TE) in soils of Brazil.” Uberlândia, Brazil. July 31- August 05, 2011. Jaime W. V. Mello

WE-Heraeus Summer School 2011 – Computer Simulations on Nanotechnology for the Environment. “Chemical speciation, nanostructured aluminosilicates and reactivity of sulfide mineral surfaces – Applications in mining and waste treatment”. July, 3-15, 2011. Hélio A. Duarte

6th International Seminar on Copper Hydrometallurgy – Hydro Copper 2011. Plennary Session: “The effects of pyrite inclusions, dissolved oxygen, and ferric ion on chalcopyrite electrochemistry”. Vina del Mar, Chile. July, 2011. Daniel Majuste

READE Seminars (Network of Remediation and Rehabilitation of Degraded Environments). “Functions of articulation of cooperation by the Mineral and Metallurgical Center of Excellence”. Évora, Portugal. June, 15, 2011. Renato Ciminelli

Chemist’s Day Celebrations – Universidade Federal de Uberlândia. “Chemistry, institutions, minds and technological innovation”. Uberlândia, Brazil. June, 17-18, 2011. José Domingos Fabris

Physics Institute of the Universidade Federal do Rio de Janeiro (IF-UFRJ). “Water, Biodiversity and Mining”. Rio de Janeiro, Brazil. May, 25, 2011. Paulina Maia Barbosa

42nd. Meeting AMDA (Mining Association of Environmental Defense) “Extraction of complex minerals, of low levels, and conservation of water resources and biodiversity – the search for compatibility”. Paracatu, Brazil. April, 27, 2011. Virginia S. T. Ciminelli

Department of Materials Science and Engineering – The Pennsylvania State University. “Nanostructure Aluminosilicates and Chalcopyrite Surface Reactivity – A Computational Approach” State College – PA, USA. February, 16, 2011. Hélio A. Duarte

Institute of Bioinformatics and Computation, University of Calgary – “Nanostructure Aluminosilicates and Chalcopyrite Surface Reactivity – A Computational Approach”. Calgary, Canada. February, 09, 2011. Hélio A. Duarte

Seminar on Reference Values of heavy metals in Brazilian soils. Graduate Program in Soil and Plant Nutrition – ESALQ/ USP. “Submission of partial results of reference values for heavy metals in Espírito Santo and Minas Gerais soils”. Piracicaba, Brazil. December, 06, 2010. Jaime W. V. Mello

16 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

Interaction with other projects and INCT´s CEFET-MG – IUT1 – University Joseph Fourier

CAPES/DAAD (PROBRAL) – ICEx/UFMG

Electrocoagulation as alternative for wastewater treatment. France

Nanostructured clay minerals – solutions for technological and environment challenging problems (2010- 2011).

(Université Joseph Fourier – Laboratoire d’Electrochimie et de Physico-chimie des Matériaux et des Interfaces); Brazil. (Ângela de Mello Ferreira) 2011.

CNPq/SWB/PVE- Fellowship Special Guest Researcher Massimo Gasparon – Special guest researcher of The University

BRA3013 International Agency for Atomic Energy “Providing Practical Guidance for the Implementation of a Decommissioning and Remediation Plan for the Minas Gerais Uranium Mining

of Queensland, Australia (2013-2016).

CNPq/Vale/CT-Mineral – CDTN/UFV/UFMG Characterization and Mitigation of Environmental Impacts

and Milling Production Centre” – Workshop on Treatment of

arising from Acid Rock Mine Drainage (2011-2014).

acid waters and monitoring at the Poços de Caldas uranium

Geochemical characterization of acid mine drainage –

mine – Agency: IAEA. (CDTN) 2011.

implications in the development of technologies for mitigation and mineral processing (2008-2013).

CIAM – Inter-American Cooperation of Materials

Purification of sulfuric liquors from industrial leaching

(CNPq/CONACYT/NSERC)

of nickel employing synergic solvent extraction (2011-

Cooperation between Brazil, Mexico and Canada (2009-2013).

2013).

INCT-INAMI – National Institute of Science and

CNPq/BMBF/IB/DLR – CEFET-MG/ UFMG

Technology on Nanotechnology for Integrated Markers

Development of modified clays for the removal of organic and inorganic contaminants from water (2008-2012).

Scientific collaboration and co-supervision for doctoral student. (Helio A. Duarte).

CNPq/CONACYT/NRC – ICEx/UFMG

FP7-IRSES

Materials design by multi-scale computing – Ultra-Dispersed catalysts for in situ petroleum processing – an

Exchange Program of the European Community, Computer

interamerican materials research proposal (2009-2012)

simulations of thermally excited molecules and materials by first principles (TEMM1P), involving the following countries: Germany,

FAPEMIG/PPM – CDTN

France, Italy, Spain, Brazil, Japan, Canada, and Mexico. (Helio A. Duarte) 2012-2016.

Mitigation and remediation of environmental impacts of uranium mining aiming at decommissioning (2010-2012).

FP7-PEOPLE-2011-IRSES

FAPEMIG/ University of Queensland – UFV/ CDTN/ UFMG

Exchange Program of the EUROPEAN COMMISSION, Study of

Role of Fe-Al (hydr)oxides as geochemical barrier: Mitigation of acid mine drainage and phase transformations (2011-2014).

soiling effect and glass surface modification of concentrating photovoltaic (CPV) modules: Climate influence and comparative testing – Sun on Clean, involving the following countries: Italy (leader), Spain, Russian, Brazil. (Ângela de Mello Ferreira) 20122014.

Additional Funding (App. US$ 4,5 million) AMIRA INTERNATIONAL/VOTORANTIM METAIS/ MURDOCH UNIVERSITY – DEMET/UFMG

Hydrogeological and geochemical studies of a uranium mining waste pile: alternatives for remediation or further exploration (2011- 2014).

FAPEMIG/SECTES/UFMG Center for Reference and Industrial Users Network in Advanced Mineral Characterization in the State of Minas Gerais (20112013).

KINROSS/UFMG/UFV (BRAZIL)/UNIV.QUEENSLAND/ENTOX (AUSTRALIA) Environmental and Health Risk Assessment in the Region of Morro do Ouro, Paracatu, Brazil. Phases 1 and 2 (2011-2014).

Electrowinning of Base Metals. Partners: 4 Universities and 11 global companies (2011-2014).

BRASKEM, BRASIL – DEMET/UFMG Capture and Conversion of CO2 (2011-2013).

LARGO MINERAÇÃO S.A. – UFV Assessment the risk acid drainage and environmental contamination by arsenic in the project Maracás-BA (2010 -2011).

NATIONAL AND INTERNATIONAL PARTNERSHIPS |

PELD – MCT/CNPq - ICB/UFMG

VALE/R.LAWRENCE/UFMG and GOLDER

Long-term Program on Ecological Research – Phase II – Ecological

ASSOCIATES/UFMG

processes and the conservation of biological diversity of the Atlantic

Assessment of the potential of Acid Mine Drainage Generation in

Forest in the middle Rio Doce watershed, Minas Gerais (2012-

Base Metal Deposits (2010-2013).

2015).

PETROBRÁS S/A – DEMET/UFMG

VOTORANTIM METAIS – DEMET/UFMG

Capture and Separation of CO2 from Natural Gas: Synthesis,

Effect of impurities in the Electrowinning of Zinc

Structural Characterization and Performance Evaluation of

(2011-2013)

Advanced Multifunctional Ceramic Membranes and New

Program for scientific and technological cooperation (2011-

Adsorbents (2011-2015).

2013).

PETROBRÁS S/A- ICB/UFMG

VOTORANTIM METAIS – IIEGA

The environmental quality of the sub-basins of the rivers Ibirité and Pintados: a proposal of integrated management policies for

Revitalization of the river São Francisco and study the

Ibirité reservoir, municipality of Ibirité, Minas Gerais state, South-

contamination of the sediment, water and aquatic biota (2008-

east Brazil (2008-2011).

2013).

The Upper Paraopeba Mining Region A Platform of Social & Environmental Research, and Education The most important iron ore mining territory in Brazil was selected for application and diffusion of the scientific achievements of the INCT Acqua: fundamentals, models and best practices for the sustainable development of mining territories in combination with mobilizing, structuring and innovative educational approaches.

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18 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

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This new focus of INCT-Acqua work emerged during the Forum Building the Future, in August 2011. At that event Science Applied to Development was challenged in view of the expansion of the iron ore production and its increasing environmental and social impacts in the Paraopeba region. Therefore, the agenda of INCT Acqua will now include the study of the interfaces of 0 iron ore mining with the territorial assets - environmental, cultural and social. The internationally known 0 2 660 mineral province, Quadrilátero Ferrífero, and specifically the region Upper Paraopeba (map 200 640 below), was chosen as the target territory. Territorial Qualification was established 200 DF 620 a v o 0 N a 20 as the new dimension of expertise of the INCT Acqua, which in turn 600 im L GO MG ES 200 led to new set of Mission and Vision as guidelines 580 o inh d a Brum 200 agreed by the group: 560 irito Itab J

Brás do Suaçuí. The region has in the iron mining and in the steel industry the base of its economy. The government of Minas Gerais State estimates that the region will receive, by the year 2020, private and public investments of around R$12 billion and R$2,17 billion, respectively, and expects the region to face the creation of thirty thousand jobs (direct and indirect) and a population growth of 65%, by the end of this investment cycle. As a consequence, there is a growing concern, among government agencies and local population with social and environmental impacts, and the major structural changes that the region will experience. CODAP, The Consortium for the Development of the Alto Paraopeba Region, supported by the local platform Agenda 21, articulates the governments of the 7 municipalities and engage the local stakeholders.

Renato Ciminelli, Virginia Ciminelli, Mayor Anderson Cabido launching CESUP

CESUP - The Center of Reference and Qualification for the Sustainability of the Alto Paraopeba Region was launched formally on June 1st 2012, at a ceremony in Conselheiro Lafaiete, when an agreement was signed between INCT Acqua and CODAP in the presence of the coordinator of the Center. CESUP, operating at the CODAP headquarter with a proper office, meeting room and local team, has been offering to the community, in seminars, workshops and courses, forefront knowledge with friendly methodologies. By connecting the science developed by the Institute with the needs of the region, new R&D projects are created and validated by public authorities, social organizations and local industries. It is expected that the process of capacity building of local actors will develop instruments of mediation for a participative construction of futures within a sustainable context. Through the alliance with INCT Acqua, CODAP adds to the local governance new assets as well as a channel to the State and Federal Government. CODAP created by act the local Innovation Council, the Innovation Fund and the Alto Paraopeba Scientific Network. The partnership with the Program Geopark Quadrilatero Ferrifero, official candidate to the Global Geopark Network of UNESCO induces an innovative agenda for development of the territory by the interface with various pilot and demonstrative projects associated to sustainability. The project “Environmental Impacts in the Alto Paraopeba Valey: Aquatic and Atmospheric Pollution” is being developed at the Upper Paraopeba Valley under a cooperation INCT Acqua - University of Queensland supported by Science Without Borders. Focused on water and air quality this project has as its main objectives (a) evaluation of the environmental impacts from industrial activities; (b) stakeholders qualification through environmental education and knowledge transfer; (c) proposition of methods to improve industrial practices and, consequently, reduce the environmental impact; (d) selection of remediation techniques to affected areas; (e) contribution to the establishment of new “guidelines” for the preservation of environment and human health in the region.

NATIONAL AND INTERNATIONAL PARTNERSHIPS |

educational and outreach activities

โ ข O Velho Chico (The Old Chico) - Illustrations by Demรณstenes Vargas - Text of Raimundo Carvalho - Multimodal language research, interface design, interaction design and application development by the Center of Experimentation and Research in Multimodal Systems ( FRMFA/ UFMG) and Research Group 1maginari0: Computational Poetry (Direction: Francisco Carlos de Carvalho Marinho - School of Fine Arts/UFMG). Participants: Francisco Carlos de Carvalho Marinho, Wallace Santos Lages, Pablo Gobira, Italo Travenzoli, Eder Moreira, Leticia Cherchiglia, Sandro Miccoli, Matheus Braga, Marku Ribas. https://play.google.com/store/search?q=Velho+Chico

Stakeholder engagement is essential to identifying sustainable, long-term solutions for mining territories. Productive dialog and decision-making require access to knowledge and information. The Institute calls for joint initiatives with the public and industrial sectors, as well as with the organized society, aimed at increasing building capacity, together with local industrial competitiveness and development of public policies. Ambitious initiatives have been carried out to create, enhance, and support environmental education programs at all levels. Videos, interactive games, books, and other contemporary educational tools are developed with the aim of contributing to the construction of a new ethical perspective of sustainability.

Graduate Courses Post-Graduate Degree in Watershed Management – ICB/UFMG F., Barbosa (chair) Participants: Arnola C. Rietzler, Francisco A. R. Barbosa, Carolina B. de Abreu, Magda K. B. Greco, Paulina M. M. Barbosa, Virginia S. T. Ciminelli.

Pennsylvania State University – USA. October 24-26, 2011. “Biogeochemistry of aquatic sediments”. 30 hours. Rita Fonseca, Universidade de Évora Portugal. September 19-22, 2011. Graduate Program in Materials and Electrical Engineering – CEFET-MG “Photovoltaic Cells: manufacturing technology,

Graduate Program in Metallurgical, Materials and Mining Engineering – UFMG

materials characterization of the cells and

“Surface Area and Porosity Determination”.

sul Sistema Energetico S.p.A. – CEFET-MG.

15 hours. Peter George Weidler, Karlsruhe

May, 2012.

Institute of Technology (KIT) – Alemanha.

modules”. 15 hours. Gianluca Timò, RSE Ricerca

of Geology and Ore Deposits; Mineralogy;

Graduate Program in Materials Engineering – CEFET-MG and Graduate Program in Metallurgical, Materials and Mining Engineering – UFMG

Hydrogeology. Reactions of Minerals in Acqueous

“X-ray Diffraction and Rietveld Method (XRD,

November 12-13, 2012. “Environmental Geochemistry: Principles

Systems and Environmental Impact”. 30 hours. Massimo Gasparon, The University of Queensland – Australia. June 4-6, 2012. “Advanced Oxidation Technologies for Treatment of Water, Air and Soil”. 15 hours. Marta Irene Litter, Comisión Nacional de Energía Atómica – Argentina. February 29 – March 2, 2012.” “Principles in Aqueous Processing - Interfacial equilibria and electrochemical kinetics in aqueous processing”. 30 hours. Kwadwo Osseo-Asare, The

crystallography and mathematics basis required for quantitative analysis)”. 15 hours. Peter George Weidler, Karlsruhe Institute of Technology (KIT) – Alemanha. March 15-21, 2012. Graduate Program in Materials Engineering - CEFET-MG “Modification and Functionalization of Surfaces: preparation, structuring, characterization and application”. 15 hours. Hartmut Gliemann, Karlsruhe Institute of Technology (KIT) – Alemanha. November, 2010.

EDUCATIONAL AND OUTREACH ACTIVITIES |

Short Courses

Cycle of lectures and workshops

“Biodiversity in mining areas and the challenge of sustainability”

Regina Pinto de Carvalho

National Science and Technology Week 2011. Francisco Barbosa (organizer), Universidade Federal de Minas Gerais – Brazil. October 17-19, 2011 “Computer Simulations on Nanotechnology for the Environment” Hélio A. Duarte, Jacobs University, Bremen – Germany. July, 03-15 , 2011.

Knowledge Transfer to Society, Elementary and Secondary Schools CESUP Center of Reference and Qualification for Sustainability in the Upper Paraopeba Valley was established by INCT-Acqua in June, 2012. Several seminars, lecture cycles, forums, workshops, and technical meetings were organized. Project: Traveling with the environment Text preparation on Biodiversity, Water and Mining, broadcasted on bus lines in the city of Belo Horizonte. Funding: FAPEMIG and PROEX / UFMG. It is estimated that about 5,000 people had access to the texts. The Water School and the Aquamundo Project Projects developed by International Institute of Ecology. After the implementation of the Water School in some cities, this new and innovative idea was to create a mobile water school – Aquamundo Project - that delivers the message to the general

“The Water in the World and The Earth Globe”. UFSJ, São João Del Rei, Brazil. November, 2011. “The Terrestrial Globe under the eyes of Physics”. PUC SP, São Paulo, Brazil. November 07-11, 2011. “The Earth Globe Under the Gaze of Physics”. PUC-SP, São Paulo, SP November, 2011. “Workshop: Metals and Minerals”. UFMG, Belo Horizonte, Brazil. October, 2011. “The Water in the World / Physics and Water”. Univates, Lajeado, Brazil. October, 2011. “The Water in the World and the Physics with Water”. UFV, Viçosa, Brazil. September, 2011. “Water and Physics”. Rafain Hotel, Foz do Iguaçu, Brazil. June, 2011. “Water, Biodiversity and Mining”. UFRJ, Rio de Janeiro, Brazil. May, 2011 (Invitation of Prof. Deise Miranda Viana). “Stages of Gold Mining / Metals and Minerals” UFSJ, São João del Rei, Brazil. May, 2011. (Invitation of Prof. John Anthony Correa Filho). “The Water in the World”, Manaus, Brazil. January - February, 2011; PUC-MG, Belo Horizonte, Brazil. October, 2011; UNED Petrópolis Campus, Brazil. November, 2011; UFSJ, São João Del Rei, Brazil. November, 2011.

José Galizia Tundisi “The Limnology as a tool for science communication and science education”. XIII Brazilian Congress of Limnology. Natal, Brazil. September 4-9, 2011. “Eutrofization”. FEEVALE University State Congress of Botany, Novo Hamburgo, Brazil. June, 2011.

public, school children, and schoolteachers (see

Paulina Maia Barbosa

highlight below).

“Water, Biodiversity and Mining”. Physics Institute of the Federal University of Rio de Janeiro (UFRJ-IF). Rio de Janeiro, Brazil. May 25, 2011.

Week of Science and Technology 2012 Biodiversity, water and mining. Stand where it was presented a book. October 17-20, 2012. Workshop on Integrating Actions and Projects in Serra da Moeda Serra de Ouro Branco Circuit. Geopark Quadrilátero Ferrífero. April 11, 2012.

José Galizia Tundisi Contribution on Water and Health and Education for Science to the Group G8+5 Meeting received by President Sarkozy and forwarded to the other Chiefs of State, February 2011, France.

22 | ANNUAL ACTIVITY REPORT 2013 — INCT-ACQUA

Francisco Antônio R. Barbosa and Paulina Maria Maia Barbosa “Threat to Biodiversity in BH Neighborhood: Causes and Consequences”. 5th Summer Festival. Faculty of Economics – UFMG. March 4-8, 2011. “Mining, water and biodiversity within the project BioZoon15”; Week of Technology 2012. October, 17, 2012.

Workshop on Health Risk Assessment – Kinross, Paracatu - MG Jack Ng (speaker). November, 2011.

Awards Massimo Gasparon Received the Award for Excellence in Teaching and Learning - University of Queensland, Australia. October 31, 2011.

Marta Irene Litter, Virginia S.T. Ciminelli et al. Received the Mercosur Award of Science and Technology for the work “El problema del arsénico en el MERCOSUR. Un abordaje integrado y multidisciplinar en La investigación y desarrollo para contribuir a su resolución”. November, 2011.

Daniel Majuste Best thesis in 2011 from the Graduate Program in Metallurgical, Mining and Materials Engineering: “Oxidation of chalcopyrite: Investigation of the electrochemical mechanism via in situ and ex situ X-ray diffraction using

synchrotron radiation and quantification of the pyrite association galvanic effect”. Advisors: Virginia S. T. Ciminelli and Kwadwo Osseo-Asare (PSU, USA), October 2012.

José Domingos Fabris (i) ISIAME2012 Poster Award “FeOOH: An efficient photocatalyst for the molecular splitting of water using sunlight the radiation source” in the International Conference on the Industrial Applications of the Mössbauer Effect (ISIAME), Dalian, China, September, 2-7, 2012. (ii)UFMG Theses Grand Prize, Diana Quintão Lima de Oliveira (“Oxidative Degradation of organic compounds in aqueous medium by catalytic heterogeneous magnetite and goethite doped with niobium,” 2011; Graduate Program in Chemistry; advisor: José Domingos Fabris), Federal University of Minas Gerais; October 18, 2012.

The 16-17 year-old students, Nayara Nogueira Soares Marra and Rafael Cavalcanti Lembi (Technical Courses in Chemistry and Environmental Science of CEFET-MG), were the recipients of many awards at scientific events attended in 2011 and 2012, with the project “Phytoremediation and biomonitoring of water contaminated by Chromium”. The supervisors, Professors Andréa Rodrigues Marques Guimarães and Angela de Mello Ferreira, highlight the support from INCT-Acqua for the young scientists program at CEFET-MG and for the research program of this institution. • 3rd Place in the I - Sweeep - International Olympiad on Sustainable World (Energy, Engineering and Environment), Houston, EUA. • FAPEMIG Honorable Mention. • XXII META in the Biological Sciences category - (1st place). • UPF Agricultural Innovation Award. • The 2012 Regional Ricoh Sustainable Development Award. • MOSTRATEC (Novo Hamburgo/RS); Cientec (science exhibition, 2012, in Lima/Peru). • FEBRACE (Brazilian Exhibition of Science and Engineering, 2012 , São Paulo, Brazil.

Left:. Prof. Andréa Rodrigues M. Guimarães, Students Rafael Cavalcanti Lembi and Nayara Nogueira S. Marra, and Prof. Angela de Mello Ferreira. Right: Students Nayara Nogueira S. Marra and Rafael Cavalcanti Lembi.

EDUCATIONAL AND OUTREACH ACTIVITIES |

Products and Educational Materials Website

http://acqua-inct.org. INCT- Acqua website, with updated news from the Institute.

Videos

Innovation Pathways Program (USP-IFSC) – Estojo 2, DVD3 – “Innovation: Scientists Vision” – interview of Virginia S.T. Ciminelli. 2011. Short Course “Surface Area and Porosity Determination”. Peter George Weidler (Karlsruhe Institute of Technology (KIT) – Alemanha), UFMG, Brazil, November 12-13, 2012.

Printed media, digital games and installations

Tundisi, J. G.; Tundisi, T. M. “Teacher’s Notebook – Aqua Mundo Project”. São Carlos: IIE, 2012. Guimarães, L.N.; Machado, I.C.; Maia-Barbosa, P.M. “Discovering Mining” - identification of technologies / methodologies that can be transferred to society. Guimarães, L.N.; Machado, I.C.; Maia-Barbosa, P; Barbosa, F.A.R; Rietzler,A; Sant’Ana, E.E. - Folders “Mining”, “Limnology and the Way of the waters”. Science and Technology Week. October, 2012. Guimarães, LN; Machado, I.C.; Maia-Barbosa, P; Barbosa, F.A.R; Rietzler,A; Sant’Ana, E.E. - Banners: “Knowing minerals”, “Climate Change and Biodiversity”, “Where are our waters”. Guimarães, L.N.; Machado, I.C.; Maia-Barbosa, P. - Game: “Biodiversity” - game for elementary school chidren working with animal biodiversity of various biomes of Brazil. Guimarães, L.N.; Machado, I.C.; Maia-Barbosa, P; Campos, LA. - “Hangman game on Mining” - digital game for elementary school children addressing the Mining as a subject. Maia-Barbosa, P; Barbosa, F.A.R. - 2D Animation – “Mining and Biodiversity” – animation showing the use of water in mining different stages and some of its impacts. Francisco Carlos C. Marinho et al. - “Man - Nature” - Man- Nature is an interactive computational art installation, whose theme is linked to the concept of sustainability and the environment. It consists of a series of video-chronicles and hypertexts that describe, in a concise manner, the history of the relationship between man and nature, seen from the perspective of western rationality - science/Greek philosophy to contemporary complexity theories. The installation shows the key moments of the rupture of Western thought concerning nature. In Greece, it shows the passage from myth to logos – the desecration of nature. Israel Pinheiro Space (an exhibition created by an agreement between UFMG and Israel Pinheiro Foundation). Francisco Carlos C. Marinho et al. - “Interactive Ecology “ - This computational art installation focuses on the environment as its subject. It is a facility that uses a tangible interface - table/multitouch monitor, developed by the Group 1maginário: poéticas Computacionais. The content is a digital world in which virtual creatures (pictobiobots - robots with digital pictorial forms), created at runtime by users, reproduce and compete for resources. Each creature has its own behavior defined by its visual structure (size, shape, color), which determines the parameters, such as speed and energy expenditure. The digital environment, understood as a pedagogical and aesthetic element, empowers users with a sensory/perceptual experience on topics such as morphogenesis, predator prey behavior, environmental change under the influence of human action, and competition for scarce resources. The idea is that the facility, in addition to being an artistic work, also represents a means through which to disseminate scientific training geared toward the general public, especially toward children. The facility has a playful approach and can be characterized as a digital “game” education. This work is part of the UFMG Collection of Knowledge Space - TIM. Website http://acqua-inct.org. INCT- Acqua website, with updated news from the Institute.

Institutional Material Newsletter INCT-Acqua

News for Radio Broadcast and Magazines

1 Catalog of INCT-Acqua | 3 Folders | Portfolio Briefcase | 1 Annual Report (2009-2010) 1st Edition – July, August and September, 2012. 2nd Edition – October, November and December, 2012. Public Information Office - Established in 2012. Magazines and Newspapers: 06 Newsletters: 03 Radio: 03 TV: 01 Websites: 37 Highlights: UFMG website. October 22, 2012 – “Reconversion of mining territories mobilizes researchers and public managers” by Renato Ciminelli. UFMG Newsletter. July 02, 2012 – “In details”, about the equipment Mineral Liberation Analyzer (MLA) by Virginia Ciminelli. Brasil Mineral Magazine. N 319, page 10. Special Edition, 2012. “CODAP sign new agreements” by Renato Ciminelli and Virginia S. T. Ciminelli. Estado de Minas website. June 19, 2012 – “Sustainability projects will be taken to Rio +20 by UFMG”. EPTV TV Jornal. June 05, 2012 – “Aqua Mundo Project” by José Galizia Tundisi. IBRAM – Brazilian Mining Association website. June 01, 2012 - “Cooperation between institutions aims sustainable development of mining area” by Virginia S. T. Ciminelli. Veja Magazine. December 21, 2011- Comment about Belo Monte Hydroelectric and the article“Knocked out by logic” by José Galizia Tundisi. Mineria Chilena magazine. July, 2011- News about the paper presented by Daniel Majuste in the 6th International Seminar on Copper Hydrometallurgy – Hydro Copper 2011, Vina del Mar, Chile - “The effects of pyrite inclusions, dissolved oxygen, and ferric ion on chalcopyrite electrochemistry” by Daniel Majuste. UFMG website. April 07, 2011 - “José Galizia Tundisi, ex-president of CNPq, talks at UFMG about Brazil’s contribution to the G8 meeting” by José Galizia Tundisi.

24 | ANNUAL ACTIVITY REPORT 2013 — INCT-ACQUA

The Mobile Water School - AQUAMUNDO The Water School was a Project developed by the International Institute of Ecology - IIEGA. The project began 10 years ago with the basic idea of providing citizens, students and schoolteachers with information about water. With the understanding that biodiversity, the lives of human beings, and the functioning of the biogeochemical cycles depend upon the water available and its quality, the message was: what protects and enhances human life? What are the impacts of human activities on the life-support systems, considering that water is a key substance? After the implementation of the project in specific cities, the new and innovative idea was to promote a mobile water school vehicle that could deliver the message to the general public schoolchildren, and schoolteachers. Four basic processes are shown: the hydrologic cycle; biodiversity; the watershed as a unit; the pollution and degradation of surface and underground waters. The mobile water school was organized in a truck with a large area for installing interactive midia, such as touch screen panels, games, and other information on the above topics. To date, 30 municipalities in the states of São Paulo and Minas Gerais were visited. A total of 10,000 people have visited this facility. They were received by a group of monitors that were trained to provide detailed information on the subjects described above. Parallel conferences with schoolteachers complemented the activity. A total of 400 schoolteachers participated in the capacity building program; this program aimed to provide the teachers with tools to improve and enhance their capability of transferring knowledge. A teacher’s guide to enhance the overall outreach of the project was produced and distributed as a support to the visits and to stimulate the use of these ideas in the

Students and school teachers at the truck AQUAMUNDO

classroom. This project began in 2012 and is in full progress. The mobile water school is expected to visit 250 municipalities in five years with a total population involved of approximately 7 million people. TV programs are part of the project in an attempt to enhance and extend the outreach capacity of the project and its extension.

Scientists visiting the AQUAMUNDO

Barretos, SP- School children at the AQUAMUNDO with monitor

This project is a joint venture of IIEGA – INCT ACQUA with other private and public institutions: EPTV Education Institute, SABESP, FINEP, Transportadora Americana, Universidade FEEVALE.

EDUCATIONAL AND OUTREACH ACTIVITIES |

science highlights

28 research topic 1 Assessment of water/environmental quality and aquatic biodiversity

60 research topic 2 Modeling and simulation of hydrometallurgical processes

76 research topic 3 Natural and synthetic materials for environmental and technological applications

86 research topic 4 Acid rock drainage

science highlightsâ&#x20AC;&#x201A;|â&#x20AC;&#x201A;

research topic 1

Assessment of water/environmental quality and aquatic biodiversity 30

Scientific tools for a comprehensive environmental and human health risk assessment in gold mining areas

Bioaccumulation of arsenite and arsenate in cyanobacteria

Arsenic differential toxicity in two cultured Cyanobacteria species

Plankton diversity and environmental quality in mining areas

Molecular diversity of prokaryotes in mining-impacted and non-impacted streams and bacteria and genes involved in arsenic speciation

Ecotoxicological assessment of soils around mining areas

Comparison of zooplankton community biodiversity in lentic and lotic environments of the S達o Francisco river

Biodiversity of benthic macroinvertebrates in the metal contaminated River S達o Francisco (middle course)

Diatom assemblages as indicators of water quality in lotic systems: new approaches for river management

SCIENCE HIGHLIGHTS SCIENCE - RESEARCH HIGHLIGHTS TOPIC 1 |

Scientific tools for a comprehensive environmental and human health risk assessment in gold mining areas V. S. T. Ciminelli1,*, M. Gasparon2, G. C. Silva1, J. C. Ng2, P. R. P. Paiva3, A. M. Ferreira3, P. G. Weidler4, E. T. F. Freitas5, M. A. Morais6, J. M. Esper6, A. L. Nepomuceno6 1 Department of Metallurgical and Materials Engineering - Universidade Federal de Minas Gerais (UFMG) Belo Horizonte, Brazil 2 University of Queensland - UQ - Brisbane, Australia 3 Centro Federal de Educação Tecnológica de Minas Gerais - Belo Horizonte- Minas Gerais 4 Institute for Functional Interface (IFG) at Karlsruhe Institute of Technology KIT 5 Center of Microscopy at the Universidade Federal de Minas Gerais 6 Kinross Brasil Mineração - KBM - Paracatu, Brazil *Corresponding author: ciminelli@demet.ufmg.br – Departamento de Engenharia Metalúrgica e de Materiais, Universidade Federal de Minas Gerais; Av. Antonio Carlos, 6627- CEP 31270-901, Belo Horizonte MG, Brazil

Keywords: arsenic speciation, gold mining, Rietveld, isotope analyses, Synchrotron light X-ray absorption spectroscopy, environmental and health risk assessment.

Arsenic mineralization associated with a gold mine in the vicinity of Paracatu, Brazil, is well documented. Due to concerns regarding potential environmental and human health risk associated with As natural occurrence in the Morro do Ouro Mine (Figure 1), studies were performed to objectively assess the impact of natural background conditions as well as gold mining activities on the nearby environment and community. The objectives of this investigation are to (i) rigorously determine the environmental natural conditions (background), sites, materials, and processes that may lead to mobilization of arsenic (and other metals) following all activities carried out at the mine site (mining, mineral processing, hydrometallurgy and waste storage), now and in the foreseeable future; and (ii) investigate the possibility and processes whereby any arsenic (and other metals) mobilized by the mine’s operation may reach the community by air, water, soil/dust and food. The approach and the analytical methods described here provides not only a scientifically rigorous and comprehensive assessment of the current situation at this specific site, but also its ultimate goal is to provide abroad and solid understanding of any potential risks related to the potential availability and mobility of toxic trace elements from a mine site, as well as information

30 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

on other potential sources of contamination, both natural and anthropogenic. The knowledge will be applied to other mining regions of INCTAcqua’s research interest.

Evaluation of arsenic mobilization The first example describes the use of geochemical tools to improve the existing hydrogeological concept model of the site. The impact of mining operation on water quality and quantity is a key issue for all stakeholders. The isotopic analyses allow one to establish the potential hydraulic connectivity between surface and groundwater, hydraulic permeability, and groundwater velocities. These tools also help the prediction of the velocity of propagation of any leakages of mine water, and the definition of the best and most cost-effective methodology for the monitoring of surface and groundwater quality. To achieve these results, a combination of oxygen and hydrogen stable isotope, and natural 222-Rn tracing methods were used. As an example, the results shown in Figure 2 depict the variation in222Rn concentrations in different water samples, which in turn indicate different rates of aquifer recharge across the site.

The second example focuses the dispersion of arsenic as particulate matter in the atmosphere. Arsenic dispersion is being monitored using a combination of active and passive samplers, which allow determination of bulk arsenic content in the dust, as well as the distribution of arsenic in different mineral phases and non-mineral matter by single particle analysis. The distribution of arsenic obtained with a special sampler designed for single particle analyses using Scanning Electron Microscopy and Energy Dispersive X-Ray are shown in Table 1. The results indicate major arsenic association with silicates (less mobile As) and with carbonaceous material. The latter provides an evidence of wood combustion (bush fires) as a source of arsenic in the particulate matter in the atmosphere. The mineralogical characterization of airborne dust from mining and nearby urban regions provides essential information for monitoring and evaluation of environmental impact. Various samples of dust, soil and from the orebody have been submitted to X-ray diffraction (XRD) with Rietveld refinement. The latter is a method to

Figure 1. Morro do Ouro mine in Paracatu with an inset showing the location in the state of Minas Gerais, Brazil.

accurately identify and quantify the mineral phases present in the different solid matrixes. The results from the analyses of an ore sample and an airborne sample collected 2 km far from the mine are shown in Figure 3. The mineralogy regarding the essential minerals is very similar, with muscovite and quartz accounting for 60% to 80%. Nevertheless, the presence of calcite and dolomite and a broad band of an unknown amorphous phase combined with the absence of siderite and arsenopyrite phases (Figure 3) indicate that mining is not the solesource of the dusts. The diffraction patterns also provide individual fingerprints, which become useful tools for tracking the sources of particulates. The method has been applied to dust/soil characterization in the mine area. The third example involves the application of advanced spectroscopic techniques to investigate the mobilization of arsenic from tailings dam. Light synchrotron, X-ray absorption spectroscopy analyses (XAS) have been applied to identify the molecular configuration of arsenic association with different substrates in the environment. The analyses of As-sulfide tailings and the soil liners (oxisol) from special tailings storage tanks has the aim to anticipate contaminant dispersion from the tailings impoundments. The XAS analyses combined with other methods showed that arsenic is present in its more reduced form (arsenopyrite) and also as As(V) species in the As-sulfide tailings (Figure 4). This result implies that minor oxidation of arsenopyrite (the main arsenic phase in the tailings) took place over more than 15 years of impoundment. The low As concentration in the pore Table 1. Distribution of arsenic in different mineral and non-mineral phases of atmospheric particulate matter determined by Scanning Electron Microscopy and Energy Dispersive X-Ray Analysis.

Grain Type*

Figure 2. Relationship between bore depth and 222Rn concentrations, showing different rates of aquifer recharge.

% of Approximate Arsenic grains Content in grains (%)

Arsenopyrite

0.0

N.D.

Carbonaceous

38.1

0.8

Silicate

53.4

0.5

Carbonate

5.6

0.6

Fe-rich

2.6

0.5

Sulphide and Sulphate

0.32

0.6

Unknown

0.03

0.0

*Total of 3446 grains analyzed; N.D. not detected.

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 1 |

waters, both in the oxisol and in the tailings, was another indication that dissolution has not occurred. The association of arsenic with the oxisol was investigated with high-resolution transmission electron microscopy (HR-TEM). Arsenic was found in nanoscale crystalline phases containing iron and aluminium. From Electron Microdiffraction analyses performed using TEM, it was established that the crystalline phases containing arsenic are mainly goethite and gibbsite (Figure 5). These unique structures are likely to be secondary phases and may explain the the low mobility of arsenic and its association with Fe(III)- enriched crystalline phases, indicated by sequential extraction analyses.

Health Risk Assessment Health Risk Assessment for arsenic is based on the population exposure considering all pathways, such as ingested (water + food + soil/dust) and inhaled As (dust), as dermal exposure is known to be negligible (Figure 6).

The measured arsenic exposure is compared to the Benchmark dose BMDL0.5 established by the World Health Organization and the United Nations Food and Agriculture Organization Joint Expert Committee of Food Additives (JECFA, 2011). In order to calculate the ingested and inhaled arsenic, surveys were conducted around Paracatu town in close proximity of the Kinross Brasil Mineração (KBM) gold mine site. Samples of water, dust, atmospheric particulate matter and food were collected. The results demonstrate the low arsenic intake via drinking water, which is consistent with the conclusion that mining operations have not impacted on the Paracatu drinking water quality over the years of operation. The bioaccessibility (BAC) concept was applied in this investigation to provide a more realistic uptake of arsenic from soil/dust. BAC refers to the fraction of a compound that is soluble in the gastrointestinal tract and is therefore available for absorption – which is specifically referred to when in-vitro assessment models are used (Ng et al., 2010). BAC is often applied in a Risk

Figure 3. X-Ray diffraction patterns with Rietveld refinement of an ore and an airborne dust samples.

32 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

Assessment process for a conservative estimation of bioavailability (BA), which is the amount of a contaminant that is absorbed into the body following skin contact, ingestion, or inhalation, determined in-vivo. The BAC value found in this study(3.4±2%) for arsenic is in agreement with that of 4.2% reported by Ono et al. (2012) in samples collected near the mine site. Our investigation comprised a major food survey. The results demonstrated that the highest arsenic concentrations are found in rice and beans (not locally produced) and consumed daily in higher amounts than the other food items. Rice

is recognized as a significant source of inorganic arsenic especially in Asian countries and other countries (JECFA, 2011), especially where rice is a staple food, such as Brazil. For a realistic health risk assessmentit is important to know the inorganic arsenic components (iAs) of the total arsenic intake, as iAs species are more toxic than the organic species. Arsenic speciation in rice is illustrated in Figure 7. Typically rice tends to have higher levels of iAs with little DMA (dimethyarsinic acid, dimethylated arsenic). The overall results indicate that despite the occurrence of arsenic lithologies in the area, local geology and mining activities have a minor impact on the total arsenic exposure in Paracatu. The exposure follows a pattern similar to that found in the US and Europe, where the dietary intake is reported as the main source of exposure. Considering all sources, the risk associated with the exposure - 0.44µg/kg/day for adults and 0.36 µg/kg/day for children - was found approximately 11 times lower than the Benchmark dose BMDL 0.5 of 3µg/kg/day. The results of independent epidemiological studies (CEMEA, 2012) also demonstrate that the incidence of diseases in Paracatu (including cancer, neurological

Figure 4. Arsenic forms in solids (tailings) determined by Light Synchrotron X-Ray Absorption Spectroscopy. The As(V) was ascribed to scorodite, a ferric arsenate mineral present in the ore.

symptoms, and respiratory and cardiovascular diseases) is similar to that of other cities in the region and to the average values in Minas Gerais (MG).

Figure 5. Arsenic association to nanocrystals of Al and Fe hydroxides in the clay samples.

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 1 |

Our study shows that a comprehensive and

to positive outcomes both for the community and

rigorous scientific approach to environmental and

the mine operator. Sound scientific information

human risk assessment in mining regions can lead

helps to create an open dialogue and actions that result in better and more cost-effective management practice and benefits in terms of human and

Table 2. Total daily arsenic exposure.

Source

Arsenic Exposure

Water Ingestion

Dust/Soil Ingestion

Dust Inhalation

Food Ingestion

90%

environmental health, and public policies.

Acknowledgments The Center of Microscopy at the Universidade Federal de Minas Gerais (http: //www.microscopia. ufmg.br) is acknowledged.

Figure 6. Population exposure pathways for arsenic.

Figure 7. Different arsenic species in rice determined by Atomic Fluorescence Spectroscopy.

References C E M E A (2 012). C e n t ro M i n e i ro d e E s t u d o s Epidemiológicos e Ambientais - CEMEA. Perfil de morbimortalidade em municípios da região de Paracatu. Relatório Técnico, 26p.

NG, J.C., JUHASZ, A.L., SMITH, E., NAIDU, R. (2010). In: CRC CARE Technical Report 14. CRC for Contamination Assessment and Remediation of the Environment, Adelaide, Australia, 74 p.

JECFA (2011). Evaluation of certain contaminants in food. The seventy-second report of Joint FAO/WHO Expert Committee on Food Additives. WHO, 115 p.

ONO, F.B., GUILHERME, L.R.G., PENIDO, E.S., CARVALHO, G.S., HALE, B.,TOUJAGUEZ, R., BUNDSCHUH, J. (2012). Environ. Geochem. Health. 34(4), p. 457-65.

34 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

Bioaccumulation of arsenite and arsenate in cyanobacteria

M. W. Franco1; F. A. Guedes1; D. Oliveira1; S. M. S. Magalhães2; F. Barbosa1* Laboratory of limnology and aquatic ecotoxicology – Institute of Biological Sciences - Federal University of Minas Gerais (UFMG), 31-270-901 - Belo Horizonte, Brazil 2 Social Farmacy – School of Farmacy (UFMG) *Corresponding author: barbosa@ufmg.br, Av. Antonio Carlos, 6627, CEP 30270-901, Belo Horizonte, MG, Brazil 1

Key-words: Arsenic speciation, bioaccumulation, cyanobacteria.

Arsenic bioaccumulation occurs in different positions in the food chain, from primary producers to top consumers, so the process of biomagnification follows through different routes. Phytoplankton species possess the property of bioaccumulation of metals and can transfer them to the second trophic level, thereby increasing the exposure sources of this element (Parven et al., 2009). Arsenic toxicity is strongly related to its chemical species. For this reason it is important to investigate the bioaccumulation of arsenate and arsenite, which are the two most common chemical species of arsenic in superficial and ground waters. In this study it was investigated the bioaccumulation of arsenite and arsenate by Synechococcus nidulans, a non-toxic cyanobacterium species widely distributed in fresh water, isolated from water samples collected in a water course contaminated by the semimetal arsenic (As) and other heavy metals, in Nova Lima – MG. Cyanobacterial cultures were exposed to arsenate and arsenite treatments. Experiments with arsenate were conducted in two geometrical series: a) 0; 0.05; 0.5; 5; 50 mg.L-1 and b) 500; 900; 1620; 2916 mg.L-1. The first represents lower concentrations, near environmental levels, and the second covers the toxicity arsenate level. Arsenite experiments were conducted in concentrations of toxicity (4.8; 5.5; 6.3; 7.3 mg L-1). Arsenic determinations were performed after 96 h of exposure, in triplicate, by ICP-OES (inductively coupled plasma optical emission spectrometry). For arsenate, the results indicate the proportion of arsenate bioaccumulated in the biomass increased with higher levels applied (Figure 1a), and that in lower concentrations, the process of bioaccumulation occurred at higher percentages

relative to total arsenic initially applied to the culture (Figure 1b). Results for arsenite indicate a minor proportion of arsenic in the biomass in toxicity levels (Figure 2a) and higher relative percentage of intracellular arsenic (Figure 2b). Cultures bioacumulated arsenate only at high concentrations, whereas for arsenite, bioaccumulation occurred at lower concentrations. Experiments were conducted at neutral pH, under this condition, trivalent arsenic species is neutral (pKa = 9.2) and primarily present in solution as As(OH)3, whereas arsenate is charged and exhibits two chemical forms: H 2AsO 4 and HAsO 4 -2 . Synechococcus cell surface exhibits three distinct sites, corresponding to carboxyl, phosphate, and amine groups. Due to predominance of carboxyl groups cell surface is negatively charged at neutral condition (Dittrich and Sibler, 2005). Repulsive interactions between negatively charged cell surface can act as a protective barrier, thus arsenate toxicity was pronounced only at higher concentrations comparing to arsenite. Moreover, this difference in pKa is relevant for the type of transport system that catalyzes uptake of the penta- and trivalent forms of arsenic (Rosen et al., 2002). Because of the chemical similarity between arsenate and phosphate, arsenate effects are explained on the basis of phosphate biochemistry (Guo et al., 2011). However, trans-membrane movement of trivalent arsenic is conduct by aquaglyceroporins (Liu et al., 2002), a widespread protein family also present in cyanobacteria. Because of its neutral chemical nature, arsenite might be considered an inorganic equivalent of glycerol, an analog substrate for aquaglyceroporins.

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 1 |

Although a considerable theoretical knowledge on this particular field has been accumulated, arsenic fate into the cells is not yet fully demonstrated. Studies on arsenic speciation are being conducted at the Brazilian Synchrotron Light Laboratory, to clarify the arsenic binding sites into the cells. From the results obtained here, it is important to note that although the relative percentage of

bioaccumulated arsenic is relatively low, ecological studies are needed to verify the possible effects of bioaccumulation in the food chain. It is important to note that although cyanobacteria are highly resistant to adverse conditions, zooplanktonic and benthic communities consists of many sensitive species, and can suffer changes in their composition with the process of arsenic biomagnification in trophic chain.

Figure 1. (a) Total arsenic accumulated in dry biomass and (b) relative percentage of arsenic retained in biomass under exposure to arsenate.

Figure 2. (a) Total arsenic accumulated in dry biomass and (b) relative percentage of arsenic retained in biomass under exposure to arsenite treatments.

References DITTRICH, M., SIBLER, S. Journal of Colloid and Interface Science, 286, 487–495 (2005). GUO, P.;, GONG, Y.; WANG, C.; LIU, X.; LIU, J. Environmental Toxicology and Chemistry, 30 (8) 1754–1759 (2011). LIU, Z.; SHEN, J.; CARBREY, J.M.; MUKHOPADHYAY, R.; AGRE, P.; ROSEN, B.P. Proc. Natl. Acad. Sci. USA, 99, 6053-6058 (2002).

36 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

PARVEN, N.; BASHAR, M.A.; QURAISHI, S.B. Journal of Bangladesh Academy of Sciences (33), 1, 131-137 (2009). ROSEN, B. P. FEBS Letters, 529, 86-92 (2002).

Arsenic differential toxicity in two cultured Cyanobacteria species

F. A. F. Guedes¹, M. W. Franco¹, D. M. de Oliveira¹, S. M. S. Magalhães², F. A. R. Barbosa¹* 1 Laboratório de Limnologia, Ecotoxicologia e Ecologia Aquática, Instituto de Ciências Biológicas, Universidade Federal de Minas Gerais - UFMG, CEP 31270-901, Belo Horizonte, MG, Brazil 2 Departamento de Farmácia Social, Faculdade de Farmácia - UFMG *Corresponding author: barbosa@ufmg.br, Av. Antonio Carlos, 6627, CEP 30270-901, Belo Horizonte, MG, Brazil.

Keywords: Arsenic toxicity, cyanobacteria

Arsenic (As) is a toxic metalloid that

Water samples were collected from the

occurs naturally in marine and groundwater

stream Córrego da Mina just downstream a

(Smedley and Kinniburgh, 2002). Among the

mining industry at the municipality of Nova

environmental decontamination processes

Lima (19º58’74.9”S; 43º49’25.9”W), in the state

biosorption and bioaccumulation of arsenic by

of Minas Gerais and enriched in liquid BG-11

algae and cyanobacteria has the advantage of

medium. S. nidulans culture was obtained after

having low cost associated with relatively less

susceptive subculturing in solid BG-11 medium.

operating and obtaining high efficiency for

M. novacekii was isolated from water samples

trace element removal from wastewater (Arribas,

collected in Lake Dom Helvécio, the largest (6.7

2009). A large number of studies focused on

km2) and deepest (39.5 m) lake within the Rio

metal removal capability of cyanobacteria

Doce State Park, belonging to the middle Rio

but only few have directly investigated the

Doce Lake System (19º 46’419”S; 42º35’595”W)

role of the extracellular polysaccharide layer

southeast Brazil and maintained in the algae

in the metal sorption process. In several

culture bank, of the Limnology Laboratory

studies even if the cyanobacterial species

(ICB-UFMG), cultivated in ASM-1 medium.

produce mucilaginous sheaths, the presence or

The experiment was conducted under

absence of these layers had not been reported as

continuous light and constant agitation. The

pointed out by Murray et al. (2003).

arsenic source was sodium arsenate dibasic

I n th is st udy, the growth patter n of

heptahydrate (Na2HAsO4.7H2O) for pentavalent

two cyanobacteria species was evaluated:

oxidation state (As V) and sodium (meta) arsenite

Synechococcus nidulans, collected in arsenic

(NaAsO2) for trivalent oxidation state (As III),

contaminated water downstream a mining

obtained from Sigma-Aldrich. At the beginning

industry, and Microcystis novacekii, collected

of log phase As (V) treatments were applied in

in Dom Helvécio Lake, Rio Doce State Park,

triplicates, to obtain the final concentrations in

the largest remnant of Atlantic Forest in Minas

two geometric series: a) 0; 0.05; 0.5; 5; 50 mg.L-1

Gerais state. We tested growth under exposure

and b) 500; 900; 1,620; 2,916 mg.L-1. For M.

of low levels of arsenic, to evaluate the exposure

novacekii one more concentration was tested:

in phytoplankton organisms, at concentrations

5,250 mg.L-1 considering its arsenic resistance

similar to those found in real situation. Moreover,

recorded in previous tests.

in order to evaluate toxicity, higher levels were

As (III) treatment series were 4.8; 5.52;

tested in an acute toxicity test, with exposure to

6.35; 7.3; 8.39 mg.L-1 for S. nidulans and 14.7;

the arsenic oxidation states (III) and (V).

26.5; 47.6; 85.7 mg.L-1 for M. novacekii. The

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 1 |

experiment was daily monitored. Absorbance was

For As III treatments, both cyanobacteria

measured at 631 nm (S. nidulans.) and 680 nm

species presented more sensibility, reaching

(M. novacekii) were cells cultures presented an

maximum growth rate values, compared to control,

absorbance peak. Cell density was obtained using

at concentrations of 4.8 mg.L-1 (S. nidulans) and

a Fucks-Rosenthal hematocytometer.

14.7 mg.L-1 (M. novacekii) (p < 0,05) (Figure 2).

At low As V concentrations (0.05 to 50 mg L-1)

The concentration that reduces S. nidulans

S. nidulans and M. novacekii growth exhibited the

growth rate in 50% (EC50) was 3,229 As (V)

same pattern as the control (p > 0.05). However,

and 6.54 mg L-1 As (III) statistically determined

at higher concentrations growth rate decreased

and expressed by the exponential equation:

gradually (p < 0.05) and presented maximum

y = -203.151 + 31.3301*x; (R² = 0.7536) and

-1

values at concentration of 500 mg L (S. nidulans) -1

y = 263.44x – 164.79; (R² = 0.8998), respectively.

and 900 mg L (M. novacekii), compared to

For M. novacekii the recorded EC50 was

control.

considerably higher for 5,164.76 mg.L-1 As (V) and 40.99 mg.L-1 As (III) according to the equation: y= -134.935 + 21.6308*x (R² = 0.9145) and y= -144.9788 + 52.508*x (R² = 0.944), respectively. The experiments demonstrated clearly arsenic resistance of two widespread cyanobacteria Synechococcus nidulans and Microcystis novacekii as its growth rates only started to decrease at 500 mg.L-1 and 900 mg.L-1 As (V) concentration, respectively. Moreover, no effect on growth of these species was observed at similar concentrations of As (V) found in contaminated areas due to mining activities. These results are similar to those described by Shaheen et al. (2007) who pointed out that in liquid cultures Phormidium sp, two Nostoc sp, Anabaena sp. and Calothrix sp survived to

Figure 1. Test schedule arsenic toxicity to cyanobacteria M. novacekii and S. nidulans. Control (n = 4) and treatments (n = 3).

additions of arsenate up to 1000 mg.L-1. Moreover, they reported that these concentrations resulted

Figure 2. Growth rate under low As (III) concentrations, on 96 h: (a) 0 to 8.4 mg.L-1 (Synechococcus nidulans) and (b) 0 a 85.7 mg.L-1 Microcystis novacekii. Points represent mean ± SD, n=4 in control, n=3 in the other treatments. Test for co-variance analyses, p < 0.05.

38 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

in death of the cells of unicellular Aphanothece

growth rates under high pentavalent arsenic

sp. and filamentous Cylindrospermum sp. On the

exposures which were at least 100 fold the

-1

other hand, at the same concentration (1000 mg.L )

concentration used as reference value for industry

Murray et al. (2003) report stimulation of biomass

discharge (0.5 mg.L-1). Despite they present more

production in Chlorella vulgaris indicating that the

sensibility to trivalent arsenic, an oxidation state

As can play a role in selection of dominant species

more commonly in ground water.

in contaminated environments.

Although a considerable theoretical knowledge

Adsorption in cell wall must be the principal

on this particular field has been accumulated

barrier in S. nidulans for As resistance which

further studies on arsenic speciation are needed,

allowed its growth under high As level, since it has

particularly its “biological side” as performed

small cells and large volume-area ratio (Figure 3).

by cyanobacteria which has proved to be able to

According to our understanding a possible

tolerate considerable amounts of arsenic apparently

explanation for M. novacekii to resist such high

without no harm to the cells as demonstrated in

As (V) levels is due to its ability to synthesize an

this study. On the other hand, how exactly this

abundant mucilaginous sheath which also acts as

process is conducted within the cell wall is not

a barrier that prevents a direct contact of the cell

yet fully demonstrated and a targeted biological

with arsenic (Figure 4).

speciation is necessary before these organisms can

In the results here obtained both tested

be used as effective detoxicants for arsenic in the

cyanobacteria species showed no effect on their

environment, including mining areas.

Figure 3. Synechococcus nidulans cells.

Figure 4. Microcystis novacekii shows abundant mucilaginous sheath (clear areas pointed by arrows).

References ARRIBA, D. M. A. Tratamento de águas contaminadas com arsênio por adsorção em algas. Dissertação de Mestrado. Departamento de Engenharia Química. Universidade do Porto. 2009. 61pp, Porto, Portugal. MURRAY, A. L.; RAAB, A.; MARR, I. L.; FELDMANN, J. Biotransformation of arsenate to arsenosugars by Chlorella vulgaris. APPLIED ORGANOMETALLIC CHEMISTRY Appl. Organometal. Chem., 17: 669–674, (2003).

SHAHEEN, R.; MAHMUD, R.; SEN, J. A Study on Arsenic Decontaminating Cyanobacteria of an Arsenic Affected Soil. J. Soil. Nature. 1 (2): 23-29. (2007). SMEDLEY, P.L.; KINNIBURGH, D.G. A review of the source, behaviour and distribution of arsenic in natural waters. Applied Geochemistry 17, 517–568.

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 1 |

Plankton diversity and environmental quality in mining areas M. W. Franco1, P. M. Maia-Barbosa1, R. M. Menendez1, J. C. Aguiar1, D. Pujoni, F. Barbosa1,*

Instituto de Ciências Biológicas, Laboratório de Limnologia, Ecotoxicologia e Ecologia Aquática - LIMNEA, Universidade Federal de Minas Gerais - UFMG *Corresponding author: barbosa@icb.ufmg.br - Department of General Biology, Universidade Federal de Minas Gerais, Av. Antonio Carlos, 6627, Postal code 31270-901, Belo Horizonte, Minas Gerais, MG, Brazil

Keywords: Phytoplankton, zooplankton, metal pollution, bioindicator, biodiversity, mining areas

The great demand for metals and their importance to the Brazilian economy makes the

2000; Frouin and Lacobellis, 2000) and thus, may act as good bioindicators (Majer, 1987).

mining sector one of the pillars of its national

For these reasons, the evaluation of the species

economy. However, mining activity, particularly

composition of the phyto- and zooplankton

gold, moves various heavy metals and arsenic

community is a complement to environmental

from their natural deposits. This process can lead

quality assessment, bringing information from

to contamination of soil and water around mines

primary production, which cannot be obtained

causing impacts to the aquatic biota and potential

only with physical and chemical parameters.

public health consequences.

Water collections in Doce and Velhas river

In general, gover nmental monitor ing

basins, which drain the iron quadrangle were

programs in mining areas do not achieve the

sampled weekly during dry and rainy periods,

real assessment needs. Government agencies

in order to evaluate the contamination by heavy

often lack human and financial resources to

metals and arsenic in water and sediment as

perform effective supervision. Ecological studies

well as to analyze the phyto- and zooplankton

have proposed the use of planktonic organisms

communities. In each basin were chosen a

as indicators of water quality. Phytoplankton

reference area with low level of human impact,

organisms consist of species with known

and an impacted area. The four analyzed

environmental requirements and respond to

environments are located in two gold mining

changes in their habitat with changes in their

areas, in the municipalities of Nova Lima (MG)

abundance and richness. Many species have

and Santa Bárbara (MG). They are 2 small-sized

narrow environmental tolerances allowing to

streams (maximum of 5.0 meters at the sampling

infer the presence of specific environmental

point) and low depth (c. 0.50 m) with the

conditions (Azeiteiro and Marques, 2003).

influence of mines (Córrego da Mina and Barra

The zooplankton community is formed by a diverse set of organisms that play an important

Feliz); and two areas considered as “reference waters” (Mutuca and Ref.) Figure 1.

role on the aquatic ecosystems, since they are the

Physical and chemical variables and metal

center of the trophic chain of these environments.

concentrations in water and sediment clearly

Moreover, they are short life cycle, heterotrophic

demonstrate a lower environmental quality in

organisms with different shapes and sizes,

impacted areas, when compared to reference

distinct functional roles, able to rapidly answer

points as shown in principal component analysis,

to environmental changes (Purvis and Hector,

(Figure 2). Points in the impacted areas were

40 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

Figure 1. (a) Sampling areas within the Iron Quadrangle, (b) C贸rrego da Mina stream, (c) C贸rrego Mutuca stream, (d) Santa Barbara river.

grouped into distinct regions for points sampled in

the Rio Doce areas were contaminated with As

the streams C贸rrego da Mina and Mutuca (water

and Mn in water and As, Cd, Cu and Hg in the

source for the city of Belo Horizonte). Similar

sediment. Similarly, the Rio das Velhas basin

results were recorded for the study area in the Doce

showed contamination by As and Mn in water and

river basin (Table 1).

As, Cu and Zn in sediment.

The variables concentration of heavy metals

The percentage of individuals (relative

in sediment had a greater association with the

abundance) of phytoplankton taxa shows that in all

component 1, and therefore large influence in the

sampled points green algae (Chlorophyceae) were

differentiation between environments, with higher

more abundant, regardless the area was impacted

values in impacted areas (Figure 2). With respect

or not. It is noteworthy that reference areas are

to the reference values in Brazilian legislation,

regions of high environmental quality and thus with

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 1 |

lower impact of human activities. In the impacted

a higher percentage of Cyanobacteria since they

areas, the percentage of Cyanobacteria shows an

have adaptive strategies that ensure their spread

increase compared with the reference environment

in disturbed environments, such as the ability to

(Figure 3). Impacted environments tend to have

store nutrients in cytoplasmic inclusions, nitrogen

Table 1. Average values, maximum and minimum metals in water (mg L-1) at the points sampled in the Doce and Velhas river basins. Values of Pb, Ni, Cr, Al, Cd were not detected.

Reference

Barra Feliz

Mutuca

C. da Mina

Média

0,07

0,43

0,97

40,01

Máx.

0,09

1,05

1,91

0,09

164,1

Mín.

0,07

0,22

0,64

Média

0,1

1,23

1,45

45,8

0,01

Máx.

0,13

3,21

2,19

164,5

0,16

Mín.

0,25

0,68

13,27

Média

0,038

0,16

0,05

Máx.

0,06

0,16

0,05

Mín.

0,03

0,16

0,05

Média

0,04

0,77

0,84

0,15

0,12

Máx.

0,05

6,58

1,84

0,21

Mín.

0,03

0,18

0,37

0,07

Figure 2. Principal component analysis of data collected in Córrego da Mina and Mutuca streams. Metals: As, Fe, Mn, Cu and Zn in water (A) and As, Fe, Mn, Cu, Pb, Zn, Mg, Ni, Cr, Al, and Cd in the sediment (S). Physical and chemical parameters: pH, alkalinity, conductivity and total dissolved solids (TDS).

42 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

fixation, to move in the water column, and to live

species for the Nova Lima streams and 75 species

in extreme environments. Another pattern observed

for those at Santa Bárbara region) there was

in the community was a decrease in relative

dominance of representatives of two groups:

abundance of Bacyllariophyceae in impacted areas.

Protozoa and Rotifers. These are frequent in

They are very sensitive to environmental changes a

all samples, showing density peaks in some

feature considered as a potential indicator of water

periods. The participation of copepods (mainly

quality (Triest et al., 2012).

young stages) and cladocerans (more demanding

The zooplankton community from the impacted environments reflects their altered conditions: although there is a large species richness (108

groups) was very small. The genera Centropyxis and Arcella (Protozoa), and Bdelloidea (Rotifera) were dominant in both areas (Figure 4). They are widely distributed, non-specialist genera, and the latter is an indicator of environments rich in organic matter. In general, the zooplankton community of the environments located in Nova Lima showed higher species richness with higher densities. The recorded differences in composition in phyto- and zooplankton communities indicate the potential use of the plankton community as an indicator of environmental change. However in

Figure 3. Relative abundance of Phytoplancton groups (BACI: Bacillariophyta; CHLO: Chlorophyta, CRYP: Cryptophyceae, CYAN: Cyanophyceae, ZYGN: Zygnemaphyceae).

order to make this tool widely used it is necessary a standardization of regular sampling periods as well as capacity building.

Figure 4. Most frequent and abundant representatives of zooplankton communities of streams sampled in Nova Lima and Santa Bárbara (MG).

References Azeiteiro, U. M.; Marques, J. C. Acta Oecologia, 24, (2003).

Majer, J.D. 1987. Department of Conservation and Land Management, Western Austrália, 53-64.

Triest L., Lung’ayia H. Ndiritu G., Beyene A. Hydrobiologia 695, 343–360 (2012).

Purvis, A. & Hector, A. 2000. Nature, 405: 212-219.

Frouin, R. & Lacobellis, S. 2003. The absorption power of plankton. Annual report of Scripps Institution of Oceanography, 4: 2-3.

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 1 |

Molecular diversity of prokaryotes in mining-impacted and non-impacted streams and bacteria and genes involved in arsenic speciation M. P. Reis1, P. Costa1, A. Bueno1, F. A. R. Barbosa2, E. Chartone-Souza1, A. M.A. Nascimento1,*

Laboratório de Genética de Microrganismos, Departamento de Biologia Geral, Universidade Federal de Minas Gerais, Belo Horizonte, MG 2 Laboratório de Limnologia, Departamento de Biologia Geral, Universidade Federal de Minas Gerais, Belo Horizonte, MG *Corresponding author: amaral@ufmg.br - Departamento de Biologia Geral, Universidade Federal de Minas Gerais; Av. Antonio Carlos, 6627- CEP 30270-091, Belo Horizonte MG, Brazil; Tel.: +055 031 3409-2588

Key-words: arsenic, prokaryotic diversity, metagenome, tropical stream sediment.

Arsenic (As) is a ubiquitous metalloid of

some derived from gold-mining activities

both natural and anthropogenic origin, and it is

(Lièvremont et al., 2009). However, few bacterial

one of the most important global environmental

genera involved in As transformation have been

pollutants. As is often co-localized with ores of

found at any of the sites studied. Thus, a more

metals such as copper, lead and gold (Nriagu,

comprehensive knowledge on the structure

2002). Arsenopyrite (FeAsS) can be associated

of the bacterial community involved in As-

with significant amounts of gold. Accordingly,

transformation in gold-mining sites remains

the wastes from gold mining, including rocks

warranted.

and residual water, often exhibit elevated

The molecular approaches applied to

As concentrations. The contamination of

access the microbial community present in

arsenic in aquatic environments adjacent to

the sediments, included environmental DNA

gold mining operations can reach 560 µg/L

extraction (UltraClean Mega Prep soil DNA kit,

in surface waters and 5,160 µg/L in sediment

Mo Bio Laboratories); amplification of bacterial

pore waters, which is a concern because of the

(Freitas et al., 2008) and archaeal (Cardinali-

toxicity of As for human and animal health.

Rezende et al., 2009) 16S rRNA gene fragment;

Furthermore, other metal ions such as iron,

cloning of the amplicons into the vector pJET1.2/

copper, aluminum and manganese are found in

blunt (Fermentas, Canada) and transformation

mining wastewater (Lièvremont et al., 2009).

into eletrocompetent Escherichia coli XL1 Blue;

Natural mineralization and microorganisms,

phylogenetic analysis; and quantitative real-time

enhance arsenic mobilization in the environment

PCR of bacterial and archaeal 16S rDNA. For

but human interventions such as gold mining

the isolation of bacteria from sediment sample

has aggravated arsenic contamination and has

was prepared two enriched cultures with arsenite

aroused environmental and health concerns.

(As (III)) and arsenate (As (V)), separately

In nature, microorganisms have developed

(Liao et al., 2011). As(III) and As(V) resistance

different response mechanisms to metabolize

of the bacterial isolates was determined by

As, mainly via reduction and oxidation reactions,

minimum inhibitory concentration (MIC)

leading to its speciation. Previous studies

tests ranging from 2 to 512mM. Phylogenetic

have regarded As speciation as a result of

analysis of bacterial isolates was done through

microbial activity in the environment, including

the analyses of 16S rRNA sequences.

44 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

A culture-independent molecular analysis was

library. Crenarchaeal 16S rDNA sequences

performed to assess the prokaryotic diversity and

constituted 75% of the MS archaeal clones whereas

community structural changes of the tropical

Euryarchaeota were dominant in the MTS clones.

historically metal-contaminated Mina stream (MS)

Despite the markedly different characteristics

and the relatively pristine Mutuca stream (MTS)

of these streams, their bacterial communities

sediments. A total of 234 bacterial operational

harbor high diversity, suggesting that historically

taxonomic units (OTUs) were affiliated with 14

mining-impacted sediments promote diversity. The

(MS) and 17 (MTS) phyla and 53 OTUs were

findings also provide basis for further investigating

associated with two archaeal phyla (Figs. 1 and 2).

of members of Alphaproteobacteria as potential

Although the bacterial community compositions

biological indicators of arsenic-rich sediments.

of these sediments were markedly distinct, no

Moreover, a total of 123 As-resistant bacteria

significant difference in the diversity indices

were recovered from the enrichment cultures, and

between the bacterial communities was observed.

characterized phenotypically and genotypically for

Additionally, the rarefaction and diversity indices

As-transformation. A diverse As-resistant bacteria

indicated a higher bacterial diversity than archaeal

community was found through phylogenetic

diversity. Most of the OTUs were affiliated with

analysis of the 16S rRNA gene. Bacterial isolates

the Proteobacteria and Bacteroidetes phyla.

were affiliated with Proteobacteria, Firmicutes,

Alphaproteobacteria, Gemmatimonadetes and

and Actinobacteria and were represented by

Actinobacteria were only found in the MS clone

20 genera (Figure 3).

Figure 1. The phylogenetic ARB-SILVA (ribosomal RNA database) affiliation of the bacterial 16S rRNA genes. The numbers indicate the percentage representative of each phylum in the library. (A) Mina Stream sediment (MS), (B) Mutuca Stream sediment (MTS).

Figure 2. The phylogenetic ARB-SILVA (ribosomal RNA database) affiliation of the archaeal 16S rRNA genes. The numbers indicate the percentage representative of each phylum in the library. (A) Mina Stream sediment (MS), (B) Mutuca Stream sediment (MTS).

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 1 |

Figure 3. Venn diagram showing the exclusive and shared bacterial genera retrieved from MS-AsIII and MS-AsV enrichment cultures.

Most were AsV-reducing (72%), whereas AsIII-

of these genes, with arrA sequences presenting

oxidizing accounted for 20%. Bacteria harboring

phylogenetic similarity only to uncultured

the arsC gene (85%) predominated, followed by

organisms. Dendrogram analysis (data not showed)

aioA (20%) and arrA (7%).

revealed high homogeneity genetic between the

Additiona lly, we identif ied two novel

arsC and aioA sequences from the isolates and

As-transforming genera, Thermomonas and

clone libraries, suggesting that these isolates

Pannonibacter. Metagenomic analysis of arsC,

represent environmentally important bacteria, and

aioA, and arrA sequences confirmed the presence

could be acting in As speciation.

References Cardinali-Rezende J, Debarry RB, Colturato LFDB, Carneiro EV, Chartone-Souza E, Nascimento AMA (2009) Appl Microbiol Biotechnol. 84: 777-789.

Liao VHC, Chu YJ, Su YC, Hsiao SY, Wei CC, Liu CW, Liao CM, Shen WC, Chang FJ (2011) Journal of Contaminant Hydrology.

Freitas DB, Lima-Bittencourt CI, Reis MP, Costa PS, Assis PS, Chartone-Souza E, Nascimento AMA (2008) Letters in Applied Microbiol 47:241-249.

Lièvremont D, Bertin PN, Lett MC (2009) Biochimie, 91:1229–1237.

46 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

Nriagu JO (2002) Dekker, New York, pp 1–26.

Ecotoxicological assessment of soils around mining areas

R. H. Alves1, A. C. Rietzler1,*

Laboratory of Ecotoxicology, Department of General Biology, Universidade Federal de Minas Gerais - UFMG, Belo Horizonte, MG, Brazil *Corresponding author: rietzler@icb.ufmg.br - Av. Antonio Carlos, 6627, CEP 30.270-901, Belo Horizonte, MG, Brazil

Key-words: ecotoxicological assays, soils, mining areas.

Ecotoxicology is considered an important tool to assess chemical agents on the edaphic

São Francisco river basins (Nova Lima, MG) were evaluated.

community. However, studies on terrestrial

For toxicity assays, soil samples with less

ecotoxicology are recent and rare, particularly

than 2 mm were used after sifting the samples

when related to mining activities.

collected in the field. Humidity was adjusted to

Terrestrial ecotoxicological assays, already

50% of its maximum water retention capacity

standardized, usually use earthworms as

and pH was corrected to 6.0 ± 0.5, using CaCO3,

test-organisms, which deserve attention due to

when necessary.

their ecological importance. They constitute a

Avoidance assays were carried out according

source of food for a wide range of organisms,

to ISO (2008), where earthworms were placed in

play a role in the control of soil organic matter and biogeochemical cycles of nutrients, in the purification of water, in the neutralization of toxins produced by agrochemicals and in the modification of the soil structure. They are essential for the functioning of the ecosystem as well as an important resource for sustainable management of agricultural ecosystems (Jiménez and Thomas, 2003). In this context, this work aimed to assess impacts in areas influenced by mining activities

replicates containing control and evaluated soils in different hemifaces. The final distribution of organisms in each hemiface was accessed after 48 h. Acute and chronic toxicity assays were also performed, according to OECD (1984) and ISO (1998) norms, adopting mortality and reproduction of exposed earthworms as endpoints, respectively. Particle size analysis showed the same texture class for soil samples of all sampling sites, allowing comparisons of the sites and their controls. Concentrations of arsenic (Figure 1)

based on physical and chemical analyses of

were found to be higher than less restrictive

soil and toxicity studies using Eisenia andrei,

guiding values of soil quality for industrial areas

an earthworm internationally standardized.

(CONAMA resolution 420/2009, CONAMA,

Findings will enable an interface between

2009), in all samples from Córrego da Mina

ecotoxicological studies and environmental

stream (M1) and Barra Feliz (P2) sites, in contrast

surveys, evaluating the methodologies employed

with their controls, M0 and P0, respectively.

in situations involving suspicion of soil pollution by mining activities. Two areas located around regions of mining activities in Doce river (Santa Bárbara, MG) and

Rejection effects to soil samples from Mina stream and Barra Feliz were also observed in all samplings, as well as from Tulipa site (P1), in the first, second and fourth samplings (Figure 2).

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 1 |

Figure 1. Concentrations of arsenic (mg Kg-1) in the soil samples. *Values over those established by CONAMA.

Figure 2. Percentage of rejection (avoidance) of Eisenia andrei to the soils tested. *positive rejection

Regarding acute toxicity assays, no statistically significant differences were found between mortality rates of organisms exposed to the sampled soils and their controls. As for chronic toxicity tests, the number of juveniles produced by E. andrei in soil samples from M1 and P2 was statistically lower than the number of juveniles produced by their controls (Figure 3).

Figure 3. Number of juveniles produced by E. andrei in chronic toxicity tests with soil samples.

Therefore, some tests were sensitive to detect toxic effects of soils around areas with mining activity for E. andrei, showing the potential

pieces of information, including genotoxicity

impact that these sites represent to the edaphic

tests, histological changes and bioaccumulation

fauna, which may significantly interfere with

may subsidize the assessment of using terrestrial

its reproductive capacity. Thus, these and other

ecotoxicology in environmental forensics.

References CONAMA - Conselho Nacional do Meio Ambiente. 2009. Resolução nº 420 de 28 de dezembro de 2009. Diário Oficial da União de 30 de dezembro de 2009. ISO – International Organization For Standardization. 1998. ISO 11268-2. Soil quality: effects of pollutants on earthworms (Eisenia fetida). Part 2: Determination of effects on reproduction. Genebra: ISO. ISO – International Organization For Standardization. 2008. ISO 17512-1. Soil quality: avoidance test for testing the quality of soils and effects of chemicals on behaviour. Part 1: Test with earthworms (Eisenia fetida and Eisenia andrei). Genebra: ISO.

48 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

Jimenez, J. J.; Thomas, R. J. 2003. El arado natural: Las comunidades de macroinvertebrados Del suelo em lãs sabanas neotropicales de colômbia. Centro Internacional de Agricultura Tropical (CIAT). 444p. (Publicación CIAT no 336) Cali, Colômbia. OECD - Organizations for Economic Development. 1984. Guideline for Testing of Chemicals Nº 207: Earthworn Acute Toxicity Test. Paris.

Comparison of zooplankton community biodiversity in lentic and lotic environments of the São Francisco river

F. S. Soares1, R. M. Degani1, T. Matsumura-Tundisi1*, J. G. Tundisi1 Researcher of Internacional Institute of Ecology and Environmental Management. São Carlos, SP, Brazil Corresponding author: takako@iie.com.br International Institute of Ecology and Environmental Management, Rua Bento Carlos, 750. Conj. Sala C, CEP 13560-660, São Carlos, SP, Brazil 1 *

Key-words: biodiversity, Rotifera, Cladocera, Copepoda, Três Marias reservoir, São Francisco River.

The aim of this work was to compare the

material and redox potential measured in situ at

biodiversity of the zooplankton (Rotifera,

surface at the sampling stations of the reservoir

Cladocera, Copepoda) in lotic (river) and lentic

and the river downstream by using a Horiba U21

(reservoir) of the São Francisco River. Três

multiparametric sensor.

Marias reservoir was constructed by damming

The results for the surface water quality of

the São Francisco River to produce hydropower.

the two environments showed somewhat similar

In this site there were carried out zooplankton

basic environmental conditions either for the river

sampling from four stations (PR01, PR03, PR04,

or the reservoir. Only turbidity in the reservoir

PR05) distributed along the reservoir and other

was higher than in the river probably due to

four stations (PSF01, PSF07, PSF09, PSF13)

the retention of dissolved solids and suspended

were selected along the river downstream the

material in the reservoir.

reservoir as can be seen in the Fig.1. The studies

The comparison of the relative abundance

were developed between the end of 2007 and the

of the three groups of zooplankton (rotifers,

beginning of 2008.

cladocerans and copepods) between the lentic

Table 1 shows the physical and chemical

and lotic systems showed a much higher

variables such as temperature, pH, conductivity,

representation of Rotifera group in the river

turbidity, dissolved oxygen, total suspended

stations downstream than the reservoir (Figure 2).

Table 1. Water quality data measured on the reservoir (lentic) and on the river (lotic).

Reservoir

River

PR01

PR03

PR04

PR05

PSF01

PSF07

PSF09

PSF13

7.05

6.95

7.18

7.24

8.49

7.64

7.75

7.81

Cond (mS/cm)

0.099

0.087

0.093

0.108

0.062

0.296

0.073

0.067

Turb (NTU)

51.3

49.2

47.4

55.6

6.9

26.8

25.4

17.9

OD (mg/L)

9.03

8.33

8.43

7.88

8.12

7.99

8.28

8.27

Temp (ºC)

24.8

27.5

23.0

23.2

TDS (g/L)

0.06

0.07

0.04

0.19

0.05

0.04

ORP (mV)

257

277

256

240

241

291

315

322

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 1 |

Table 2. Abundance of zooplankton species: x (1-200 ind/m3); xx (201-1200 ind/m3); xxx > 1200 ind/m3).

Groups

Reservoir River

ROTIFERA

Groups ROTIFERA

Asplanchna sp.

xxx

Polyarthra vulgaris

xxx

Ptygura libera

xxx

Testudinella patina

Bdelloidea

Brachionus angulares

Brachionus caudatus

Total nº of species

Brachionus dolabratus dolabratus

CLADOCERA

Brachionus falcatus falcatus

Brachionus patulus

Collotheca sp.

xxx

Colônia sinanterina

Conochiloide coenobasis

Conochilus unicornis

Filinia longiseta

Filinia opoliensis

Hexarthra intermedia

Kellicotia bostoniensis

Keratella americana

Reservoir River

xxx

Bosmina hagmanni

xxx

Bosminopsis deitersi

xxx

Ceriodaphnia cornuta f. rigaudi

xxx

Ceriodaphnia silvestrii Daphnia gesneri

xxx

Diaphanosoma birgei

xxx

Diaphanosoma brevirreme

Diaphanosoma spinulosum

Moina minuta

Total nº of species xxx

COPEPODA

Keratella lenzi

Mesocylops sp.

Lecane bulla

Thermocyclops decipiens

xxx

Lecanea curvicornis

Thermocyclops minutus

xxx

Thermocyclops inversus

Notodiaptomus isabelae

Notodiaptomus iheringi

Lecanea luna

Lecanea lunaris Lecanea proiecta Pleosoma truncatum

x xxx x

xxx

This is a classical distribution of organisms when lotic and lentic systems are compared.

Total nº of species

of organization occurs for the Cladocera and Copepoda.

However, when the diversity of rotifers is compared

Table 2 shows the species of Rotifera, Cladocera

it is clear that in the reservoir it is much higher

and Copepoda that occur in reservoir and in river

(Figure 3).

with its abundance. As can be seen the reservoir

The reservoir has much more limnetic species

presented 21 species of Rotifera and the river 13

than the river because there are more adapted

species however the number of species that occur

species to the lentic conditions and its spatial

in high abundance (>1200 org.m3) is smaller in

heterogeneity is higher. The same structure

the reservoir than the river. In the reservoir only

50 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

Figure 1. Sampling stations distributed along the reservoir and along the S達o Francisco River.

Figure 2. Relative abundance (%) of rotifers, cladocerans and copepods found at the stations of the reservoir and the river.

Figure 3. Richness of Rotifera, Cladocera and Copepoda species found at the stations of the reservoir and the river.

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 1 |

Collotheca sp. showed high abundance. In the river

are more diverse from the spatial heterogeneity

six species (Bdelloidea, Collotheca sp, Keratella

(vertical and horizontal). Rivers collect material

americana, Pleosoma truncatum, Ptygura libera

(organic and inorganic) from the watersheds

e Polyarthra vulgaris). Among the Cladocera

rendering communities with more heterotrophic

eight species were recorded in the reservoir where

metabolism.

Bosmina hagmanni showed high abundance and

Among the factors that control and regulate

six species in the river with Bosminopsis deitersi

the structure and dynamics of zooplanckton in

in high abundance. Copepoda group presented six

rivers, there are current velocity, and dispersal of

species (Notodiaptomus iheringi, Notodiaptomus isabelae, Thermocyclops minutus, T. decipiens, T. inversus and Mesocyclops sp.) in the reservoir and two species (Thermocyclops minutus and Notodiaptomus inhering) in the river. Factors that control the spatial and temporal distribution of zooplankton in reservoirs and rivers have been studied by many authors (Huszar and

zooplankton in channels, marginal lagoons and factors that affect growth and reproduction such as food availability (Kimmel et al., 1990). Even considering that the ecosystem has hot spots of contamination by zinc industry there was not observed any relation between the composition and the abundance of zooplankton organisms and

Esteves, 1998; Nogueira et al., 2008). Accordingly

the concentration of heavy metals such as Zn, Cd

to these authors, these factors can be grouped

and Pb analyzed at the four stations (PSF1, PSF7,

in two categories: a) abiotic factors, physical,

PSF9 and PSF13).

chemical and hydrological; b) biotic factors – inter/

The exposure of the zooplankton organisms

intraspecific relationships and ecological attributes.

to contaminated water is probably relatively brief

Rivers are systems dominated by a unidirectional

due to the intense flow of the São Francisco River

flow where the horizontal movement is the main

(500m3/s). This will have a buffer effect on the

forcing function (Jorgensen et al., 2012). Reservoirs

response of zooplankton to contaminants.

References Huszar, V. L. M., Esteves, F. A. Acta Limnol. Bras. 11, p. 323-345, 1998. Nogueira, M. G.; Reis Oliveira, P. C.; Britto, Y. T. Limnetica. 2008 Jorgensen, S., Tundisi, J. G.; Matsumura-Tundisi, T. (eds). Handbook of Inland Aquatic Ecosystem Management CRC Press, Taylor & Francis, 422 pp. 2012.

52 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

Kimmel, B. l.; Lind, O. T.; Paulson, I. J. Reservoir Primary Production. In: Thornton, k.w.; kimmel, B.l.; Payne, F.E. (eds.). Reservoir Limnology: Ecological Perspectives. New York: John Wiley & Sons, 1990. p. 133-193.

Biodiversity of benthic macroinvertebrates in the metal contaminated River São Francisco (middle course)

J. G. Tundisi1* T. Matsumura-Tundisi1, R. Campitelli-Ramos1, A. M. Peret2, J. E. M. Tundisi1 , F. P. Blanco1, R. M. Degani3, F. S. Souza3 Researcher of International Institute of Ecology and Environmental Management Post Graduate Student of INCT-ACQUA 3 Fellowship student from INCT-ACQUA *Corresponding author: tundisi@iie.com.br - International Institute of Ecology and Environmental Management; Rua Bento Carlos 750, Conj. SalaC, CEP 13560-660, São Carlos, SP, Brazil 1 2

Key-words: metal contamination, São Francisco River, biodiversity of benthic macroinvertebrates, elutriate sediments, mortality rate, Amphipoda, Oligochaeta, Fish.

The São Francisco River in its middle region o

between Três Marias reservoir (Lat 18 12’ 26”

analysis of benthic macroinvertebrates sampling were carried out at the stations SF6 and SF8.

Long 45 15’ 32”) up to the confluence of Abaeté

Table 1 demonstrates the concentrations

River (Lat 18o 02’ 12” Long 45o 11’ 15”) receives

of the main metals analyzed in the sediments

the discharges of zinc processing industrial plant.

from those stations. High values of Zn were

Consequently the sediments in this stretch of the

found at the station SF4 (1732.1 mg.kg-1), SF5

river have high metal concentrations particularly

(854.5 mg.kg-1) and SF6 (765.2 mg.kg-1) and Cd

cadmium, and zinc. Limnological and ecological

at the stations SF6, SF7 and SF8 respectively

studies and the river hydrodynamics, of this river

with the values: 45.89, 22.17 and 43.74 mg.kg-1).

stretch were carried out in the last five years with the aim to prepare a diagnosis and to provide a scientific background for recovery. Sampling was made at several stations along the river (Figure 1). The collected sediment was dried and metals were extracted from the sediment. Elutriate water was extracted from the fresh sediments in order to evaluate the effect of metals on the aquatic

Based on the values of PEL for benthic organisms established by Burton (2002), only the metals Cd and Zn showed high values that could affect the development, reproduction or growth of several aquatic organisms. The response of the aquatic organisms submitted on the elutriate sediment water from the eight stations of São Francisco River varied from the organisms considered.

fauna. Metal analysis of the sediment and the

For Chironomus xanthus there were observed

elutriate water were carried out in an Atomic

the emergence rate (%) or the development of

Absorption equipment Varian AA250 FS model.

larvae to adult for the eight stations (Figure 2).

The following aquatic organisms: Chironomus

Only the experiment with the elutriate from the

xanthus (Oligocheta), Danio rerio (fish) and

sediments of the stations SF1 and SF6 showed

Hyalella azteca (Amphipoda) were submited

emergence rate higher than 60%. The site of

to the elutriate (intersticial sediment water)

SF1 where there was observed high emergence

extracted from the eight stations. For biodiversity

rate (90%) presented concentration of all metals

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 1 |

Table 1. Concentrations of the main metals (mg.kg-1) analyzed in the sediments of São Francisco River (TEL - Threshold Effect Level and PEL - Probable Effect Level, from Burton, 2002)

Stations

SF1

16.23

<LD

39.78

34.17

0.65

0.01

SF2

11.40

<LD

28.74

117.34

0.95

0.01

SF3

10.19

<LD

44.10

48.90

1.25

0.02

SF4

16.40

5.48

98.76

1732.08

1.13

0.01

SF5

20.51

2.32

79.65

854.48

0.77

0.03

SF6

11.54

45.89

44.01

765.23

1.79

0.02

SF7

17.21

22.17

32.30

284.04

0.45

0.01

SF8

19.17

43.74

41.09

238.90

0.72

0.05

TEL

52.30

0.68

30.20

124.00

7.24

0.13

PEL

160.00

4.21

112.00

271.00

41.60

0.70

Figure 1. Location of eight stations on the São Francisco River from where sediments were sampled.

54 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

analyzed lower than TFL (which does not cause any deleterious effects on the organisms).

Although high levels of metals were registered at SF6 station sediments, the results for benthic

Tables 2 and 3 refer to the mortality rate

invertebrate richness did not indicated relevant

presented respectively by Danio rerio (fish) and

differences, being almost the same at the two

Hyalella azteca (Amphipoda) exposed to elutriate

selected stations (23 and 26 taxa respectively), with

from the sediments from the same sites of São

the presence of 16 taxa occurring in both sites. And

Francisco river. For the Danio rerio after exposition for 48 hours in elutriates of sediments from the stations, only in stations SF3, SF5 and SF7 occurred 1 (one) mortality showing that the metals concentrations that occurred at the all stations do not cause deleterious effect. Nevertheless for amphipods Hyalella azteca high mortality was found in the experiments of SF2, SF3 and SF5 respectively with 60%, 70% and 50% of mortality. This mortality did not show any relation with the metal concentrations

Figure 2. Emergence rates of Chironomus xanthus larvae submitted on elutriate sediment water from eight stations of São Francisco River.

occurred on those stations. As discussed by Chapman (1992) the physiology or behavior of aquatic organisms depends upon the concentrations of natural substances and pollutants

Table 2. Experiments with Danio rerio (fish) in elutriate of sediments from sites of São Francisco river (exposure time: 48 hours).

Station

initial nº org.

final nº org.

% of mortality

affect the physiological processes of the organism.

Control

Several environmental factors can have an effect

SF1

SF2

depletion). Therefore the results obtained with

SF3

these experiments have to be considered as the

SF5

basis for further experiments that will take into

SF6

SF7

SF8

in the environment as well as the period of exposure and the time required for these substances to

on aquatic plants and animals (physical factors such as habitat alteration, sedimentation, oxygen

account the synergistic effects in the organism survival, reproduction and distribution. In the S. Francisco River several environmental factors are favorable to a lessened impact on the organisms: pH higher than 7.0; higher concentration of dissolved organic substances (gelbstoff) in the water; higher concentration of Calcium in the water. These

Table 3. Experiments with Hyalella azteca (Amphipoda) in elutriate of sediments from sites of São Francisco river (exposure time: 10 days).

Station

initial nº org.

final nº org.

% of mortality

Control

SF1

SF2

SF3

However when compared, the abundance of the

SF5

same taxon that occurred at both sites (Table 4) was

SF6

SF8

environmental conditions may attenuate the effect of metals in the organisms survival, reproduction and behavior The biodiversity of benthic organisms analyzed at two sites SF6 more contaminated than SF8, did not show a great difference in the species richness ( 23 taxa for SF6 and 26 taxa to SF8).

much higher at the more contaminated site than the less contaminated one.

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 1 |

Table 4. Benthic macroinvertebrate community composition and abundance in the sediment of two selected sampling stations. The collect was carried out in September 2010. Caption for abundance: + (1-5); ++ (6-20); +++ (21-50); ++++ (51-100) and +++++ (>100 individuals).

Taxa

Stations SF6

SF8

Hirudinea

Bratislavia sp

+++

Homochaeta lactea

Limnodrilus hoffmeisteri

+++++

+++

Limnodrilus sp

++++

+++

Conchostraca

Culicoides sp

Dasyhelea sp

Chironomus sp

+++++

+++

Cladopelma sp

Cryptochironomus sp

Polypedilum sp

++++

Stempelinella sp

Stenochironomus sp

+++

Thienemanniella sp

Pseudochironomus sp

+++

Paratanytarsus sp

Tanytarsus sp

+++++

++++

Cricotopus sp

Orthocladius sp

Ablabesmyia sp

Larsia SP

+++

Pentaneura sp

Zavrelimyia sp

Amanahyphes sp

Leptohyphes sp

Leentvaaria sp

Aphylla sp

Cernotina sp

+++

Melanoides tuberculata

Corbicula fluminea

+++

Diplodon rhuacoicus

Nematoda

56 | ANNUAL ACTIVITY REPORT 2011-2012 â&#x20AC;&#x201D; INCT-ACQUA

in general, for many taxa, great abundances were

the body undulations inside the tubes, producing

registered at station SF6, indicating that the levels

flux of water around the body (G贸mez et al., 1998).

of metals contamination obtained in this study were not sufficient to cause adverse effects on benthic invertebrates at community level. In general, the presence of tubificid worms and

From our results, we conclude that the contamination caused by heavy metals present in both studied stations are not sufficient to cause

chironomids (especially of the genus Chironomus)

adverse effects on benthic invertebrates at the

in high abundance can be associated with high

community level. But considering the high levels

organic pollution levels. These invertebrates are

of metals detected in the sediment of the studied

often the more significant proportion of benthic biomass and are the only insects, in addition to the representatives of the Order Hemiptera, that possess hemoglobin, which makes them able to

stations (especially at SF6) and the possible risks that this contamination can represent to biodiversity and human health due to cumulative

tolerate low quantities of dissolved oxygen in the

and synergistic effects the main sources of various

sediment. The gas exchanges are facilitated through

contaminations must be controlled.

References Burton, G.A., 2002 Limnology 365-375 C h a p m a n, D. ( Ed i to r), 19 9 2 U N E S C O/ W H O UNEP.585pp.

G贸mez, S., Villar, C., Bonetto, C. 1998. Environmental Pollution, 99: 159-165.

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 1 |

Diatom assemblages as indicators of water quality in lotic systems: new approaches for river management T. Bere1, J. G. Tundisi2,*, T. Matsumura-Tundisi2, F. P. Blanco2, V. T. da Silva2 Researcher of Chinhoyi University of Technology, Chinhoyi, Zimbabue Researcher of International Institute of Ecology and Environmental Management, São Carlos, SP, Brazil * Corresponding author: tundisi@iie.com.br, International Institute of Ecology and Environmental Management, Rua Bento Carlos 750, Conj. Sala C, CEP 13560-660, São Carlos, SP, Brazil 1 2

Key words: Diatom indicators, contamination, heavy metal, river management

Peryphyton communities, especially diatoms,

urban sites with very bad water quality were

constitute a system very rich in information for

characterized by Luticula geoppertiana, Nitzchia

environmental monitoring since they are one

palea and Fallacia monoculata. For laboratory

of the fundamental indicators of ecological

experiments effects of cadmium, chromium III,

conditions (quantitative and qualitative) in

lead, on natural peryphyton community were

lotic systems (Lobo et al., 2006; Bere and

studied.

Tundisi, 2010). Field studies and laboratory

A closed experimental system, consisting

experiments were conducted in order to elucidate

of three artificial streams (50cm length, 5 cm

the synergistic effects of substrate selection,

radius), each containing 6 glass substrata (6 x 15

eutrophication, organic pollution, ionic strength

cm) was used for testing the combined effects of

and heavy metal pollution on benthic diatom

metal concentration, environmental conditions

communities. Field studies were carried out in

such as light, flow, and exposure duration.

urban streams in São Carlos town. Laboratory

High metal accumulation capacity (total and

studies were conducted in experimental simulated

intracellular) by peryphyton was demonstrated

conditions at the laboratory o IIEGA São Carlos.

depending upon metal concentration, exposure

Characteristics of benthic diatom communities

duration (continuous or intermittent) and light

were analyzed in relation to contamination level

intensity. The closer the frequency and the

through general criteria (chlorophyll a, dry

duration of the pulse to a continuous exposure,

weight, ash free dry weight and cell density)

the greater are the effects of the contaminant

or specific criteria (indicator value method,

in the aquatic life. Light was shown to have a

multivariate techniques and diatom base indices).

modular effect of metal toxicant on the diatom

For field studies epilithic, epiphytic, epipsamic

accumulation capacity of metals.

and epipelic diatom communities and those

Shifts in species composition (development

growing on bricks, and natural substrates were

of more resistant species like Aulacoseira

assessed. Diatom community structure reflected

minutissima and reduction of sensitive ones

closely the decreasing water quality gradient

like Navicula sp.) were observed. Decreases in

from agricultural and forested area to the forested

species richness, and diversity and morphological

area.

alterations (deformities) of diatom cells with

Upstream sites with good water quality

increasing metal concentration and exposure

were characterized by Aulacoseira alpigena,

duration were observed. This study showed the

Stauroneis phoenicenteron. Downstream

usefulness of diatom assemblage’s conditions to

58 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

assess the water quality of streams under natural

for detection and characterization of impacts of

conditions or simulated experimental situations.

metal contamination. The research contributed

The diatom indices are an important factor for the management of river ecosystems subjected to contamination and heavy metal pollution because they can indicate hot spots of contamination or

for a better evaluation of the diatom based indices as indicator of water and sediment pollution (Potapova et al., 2005).

areas /regions in pristine conditions providing the managers with extremely relevant information to

Acknowlegements

promote planning strategies for river recovery and conservation (Morin et al., 2008). The interaction of field and laboratory experiments showed to be a useful combination

Dr. Taurai Bere thanks the Third World Academy of Sciences and CNPq for the PhD fellowship.

References BERE, T. and TUNDISI, J.G. Braz. J. Biol. vol. 70, n. 3: 493-502, 2010

MORIN, M. et al. Archiv. Env. Cont. and Toxicology, vol. 54: 173-186. 2008.

LOBO, E. A ., SA LOMONI, S., ROCH A , O. and CALLEGARO, V.L. Hydrobiologia, vol. 559, n. 1,2: 233-246. 2006.

POTAPOVA et al., J. North American Benthological Society, vol. 24:415-427, 2005.

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 1 |

research topic 2

Modeling and simulation of hydrometallurgical processes 62

Role of organic impurities in zinc electrowinning: Effects on energy efficiency and product quality

Adsorption of copper cyanocomplexes on activated carbon: Mechanisms and effects on gold adsorption

Recovery of Indium and Zinc from Computer Monitors Scrapped by hydrometallurgical techniques

Acid Rock Drainage: Impacts on the Environment and Metal Recovery

science highlights science - ReseARch highlights tOPic 2 |

Role of organic impurities in zinc electrowinning: Effects on energy efficiency and product quality Daniel Majuste1, Virginia S.T. Ciminelli1, *, Eder L.C. Martins2, Adelson D. Sousa2 1 Department of Metallurgical Engineering, Universidade Federal de Minas Gerais - UFMG, CEP 31270-901, Belo Horizonte, MG, Brazil 2 Votorantim Metais – Zinco, CEP 39205-000, Três Marias, MG, Brazil * Corresponding author: ciminelli@demet.ufmg.br – Departamento de Engenharia Metalúrgica e de Materiais, Universidade Federal de Minas Gerais - UFMG, Av. Antonio Carlos, 6627, CEP 31270-901, Belo Horizonte MG, Brazil

Keywords: zinc; electrowinning; impurities; additives.

The optimization of energy consumption

current efficiency (CE), cell voltage (CV), and

is a key issue in energy intensive processes,

energy consumption (EC) in zinc electrowinning.

such as base metals electrowinning. The

The effects of organic impurities on the

energy consumption for producing zinc, for

morphology and crystal structure of the deposits

example, accounts for approximately 25 % of

and on the mechanisms by which zinc deposition

the selling price of this metal. The electrolytic

(Eq. 1) and hydrogen evolution (Eq. 2) reactions

production of zinc accounts for about 80 %

occur were also investigated:

of the world production of the metal (ILZSG, 2012). Nevertheless, vulnerabilities still exist in the process. The present work shows that the presence of residual amounts of organic impurities in the sulfate solution may be harmful to the deposition process. The negative effects include a diminution in the current efficiency, increase in the energy consumption, and modifications of the morphology and crystal structure of the deposit, which in turn affects mechanical properties and, thus, the effectiveness of the stripping stage.

Zn2+(aq) + 2 e-  Zn (s)

(1)

+ 2 e  H2(g)

(2)

(aq)

The effects of seven organic compounds have been investigated. The experimental approach included electrochemical methods, such as electrowinning, linear sweep voltammetry and cyclic voltammetry, coupled with organic analysis by Fourier transform infrared spectroscopy and product characterization by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The effects of the lubricating oil (molecules

Due to the trend of metal extraction from low-

containing the non-polar alkyl group), which is

grade, complexes ores, it is expected a gradual

used in machinery, and the flotation collector

rise of residual amounts of organic molecules in

(molecules containing the polar amine group),

the feed solution of electrowinning tankhouses,

which is used for separating the zinc silicate are

particularly when zinc silicate ores are treated.

shown in Figure 1. In the presence of 50 mg·L-1

The hydrometallurgical route for these ores does

of the flotation collector, the average CE value

not include high temperature operations, in which

dropped from 93.7 % (organic-free solution) to

organic reagents added in prior stages, such as

21.6 %, and negative effect was also observed in

flotation, are decomposed (Majuste et al., 2013).

the presence of similar amounts of the lubricating

Therefore, the present investigation focused on

oil; CE dropped to 90.7 %. Increases in the

the effect of different organic compounds on the

average CV values and, as a result, in the EC

62 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

may be related to a strong interaction among the

that only nucleation occurs. Zinc hexagonal platelets predominantly perpendicular to the surface were observed. The deposits obtained from solutions containing the lubricating oil exhibited a large amount of pores on the surface, areas without zinc deposition, and contamination with residual organic and zinc sulfate (ZnSO4). Figure 4 shows the XRD patterns of zinc deposits obtained from organic-free solution and solutions containing the lubricating oil and flotation collector, including the corresponding preferred orientations. Only peaks for hexagonal zinc (ICDD 04-0831) were detected. The addition of 50 mg·L -1 of the collector in the solution suppressed completely the growth of planes detected for deposits obtained from organic-free solution, and the detection of the perpendicular (1 1 0) and (1 0 0) planes among the most intense X-ray reflections support the findings obtained by SEM. When the lubricating oil was added to the solution, the growth of crystals in the (1 1 4), (1 1 2), (1 0 3), and (1 0 2) directions was largely suppressed, and the growth of the pyramidal (1 0 1) and basal (0 0 2) planes was favored. The reported modifications in the morphology and crystalline structure of the product affect the mechanical properties of the deposit and, in turn, the effectiveness of the stripping stage. The findings obtained in this work led to a better understanding on the role of organic impurities in

negatively charged N atoms of the amine group

the feed solution of the electrowinning tankhouse,

values (Figure 1) were also observed when the organics were added to the solution. The voltammograms (cathodic part) obtained from solutions containing the lubricating oil, which does not interact with water molecules or charged species, indicated a significant increase of the nucleation overpotential for zinc deposition – from 74 ± 1 to 104 ± 1 mV (at 50 mg·L-1) and 114 ± 1 mV (at 100 mg·L-1), and a significant decrease of the corresponding cathodic current (Figure 2). This shifting of the zinc deposition potential in the negative direction demonstrates the polarization of the cathode, which means that the presence of this impurity in the solution has a high inhibiting effect on metal nucleation. Due to the physical adsorption of the molecules on the electrode surface, the cathodic reduction of Zn2+ ions occurs only at unblocked active sites and, thus, the current associated with the reduction of Zn2+ ions decreases with respect to that recorded from organic-free solution. Thus, a relatively high driving force is required for zinc deposition, which explains the increases of CV and EC. From solutions containing the collector, a significant decrease in the cathodic current has been observed. It decreased about 98 and 97 % at 50 and 100 mg·L-1, respectively. Such negative impact on the cathodic processes explains the drastic effect of this impurity on CE. This effect

and the Zn ions.

when zinc silicate ores are treated. The final aim

The organic impurities exhibited a marked

was to contribute for the development of best

effect on product quality (Figure 3). In the presence

practices and the reduction of energy consumption

of the flotation collector in the solution, it seems

in the industrial processes.

Figure 1. Effects of the lubricating oil and flotation collector on the average current efficiency and energy consumption values during zinc electrowinning.

Figure 2. Effects of the lubricating oil on the zinc nucleation overpotential and corresponding cathodic current.

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 2 |

Figure 4. Effects of the flotation collector on product structure. XRD patterns of deposits obtained from (a) organic-free solution; and (b) solution containing 50 mg·L-1 of the collector. (x y z) are Miller indices.

Acknowledgements This work has been developed within the scope of the AMIRA Project P705B – Electrowinning Figure 3. Effects of the organic impurities on product morphology. Back-scattered electron micrographs of zinc deposits obtained from (a) organic-free solution; and solutions containing the (b) oil and (c) collector.

of base metals, which is sponsored by 11 global industries and has the INCT-Acqua as one of the research providers.

References ILZSG – International Zinc and Lead Study Group (2012), In: Statistics; available at http//:www.ilzsg. org. Accessed on Dec, 2012.

64 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

Majuste, D., Ciminelli, V.S.T., Martins, E.L.C., Sousa, A.D. (2013), Hydroprocess 2013, Santiago, Chile.

Adsorption of copper cyanocomplexes on activated carbon: Mechanisms and effects on gold adsorption

Souza, C.1, Oliveira, A.2, De Abreu, H. A.2 and Ciminelli, V.S.T.1,* 1 Department of Metallurgical and Materials Engineering, Universidade Federal de Minas Gerais - UFMG, CEP 31270-901, Belo Horizonte, MG, Brazil 2 Group on Theoretical Inorganic Chemistry, Department of Chemistry, Universidade Federal de Minas Gerais - UFMG * Corresponding author: ciminelli@demet.ufmg.br – Departamento de Engenharia Metalúrgica e de Materiais, Universidade Federal de Minas Gerais - UFMG, Av. Antonio Carlos, 6627, CEP 31270-901, Belo Horizonte, MG, Brazil

Key-words: copper cyanocomplexes, DFT, activated carbon.

A successful extraction of low-grade, complex

intricate process. Three activated carbon samples

gold-copper ores requires a high selectivity of

with different specific surface areas (SSA)

gold adsorption on activated carbon. While the

and total density of surface functional groups

adsorption of dicyanoaurate (I) [Au(CN)2] - on

(DSFG) values were selected for the adsorption

activated carbon has been well studied, mainly

experiments: C – 1.2 µeq m-2; B – 3.4 µeq m-2;

by investigations on kinetics, reaction mechanism

and E – 5.8 µeq m -2 . Carboxylic, phenolic,

and improvements in the industrial process, the

lactones and amine groups were identified and

adsorption of copper cyanocomplexes such as

their concentrations measured. The copper

dicyanocuprate (I) [Cu(CN)2] -, tricyanocuprate

adsorption isotherms are shown as a function

(I) [Cu(CN) 3 ] 2- and tetracyanocuprate (I)

of pH in Figure 1. A higher adsorption density

[Cu(CN) 4] 3-, has received less attention and

(AD) of copper on these materials at pH 5

therefore (Davidson, 1974; Fleming and Nicol, 1984), and the mechanism of interaction of activated carbon with Cu cyanocomplexes remain unclear. In order to fill this gap, a detailed investigation of the effects of important parameters (e.g., cyanide concentration, pH, and ionic strength), on physicochemical properties of the adsorbent material has been carried out by INCT-Acqua (Souza et al., 2013).

can be seen, if compared with that at pH 10.5. The following trend was obtained (maximum values): ADC < ADB < ADE, which is linked to an increasing concentration of surface functional groups or higher amorphous character of the sample. The AD values also increased with the increase in copper concentration at pH 5. At pH 10.5, the AD values remained almost constant

The main finding of our work was a new

around 0.2-0.3 µeq m-2. The following trend for

understanding of the adsorption mechanism of

the AD values at the higher pH was obtained

copper cyanocomplexes on activated carbon.

(maximum values): ADB < ADC < ADE. At pH

The comprehension of this process has the

values below about 7.4, which represent the

aim to improve both gold extraction and the

average point zero charge (PZC) obtained for

consumption of the reagent during cyanidation.

the C, B, and E samples (Table 1), the net surface

Ma ny exper iment a l tech n iques were

charge is positive. Thus, at pH 5 the attraction

combined with Density Functional Theory

of the negatively charged Cu species by the

(DFT) calculations in order to unveil this

activated carbon samples is favored.

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 2 |

At pH 10.5, the adsorption of the negatively 2-

charged [Cu(CN)3] and [Cu(CN) 4] complexes

the [Cu(CN)3] 2- species coordinates in the anionic modified graphene through the Ca2+ cation.

decrease as a result of electrostatic repulsion, as

The most stable system formed is that formed

indicated by the lower AD values observed in

by a graphene modified with two COO- groups

Figure 1. The adsorption of copper species under

in the presence of Ca2+ cation. This system was

this condition is likely related to the interaction

the only one that presented a negative free Gibbs

with the remaining protonated basic groups. The

energy variation (∆Gf = -3.2 kcal mol-1), showing

adsorption of the tetra-coordinated complex was

that this adsorption process is thermodynamically

assumed negligible in function of a more intense

spontaneous; this complex is shown in Figure 3.

repulsion and also steric effects associated with the tetrahedral geometry.

It is important to mention that without the presence of the Ca2+ cation no stable structure

Density Functional calculations have been performed in order to describe adsorption models for Cu cyanocomplexes (as [Cu(CN) 3] 2-) in a grapheme-like structure. The model used to describe the graphene is composed by a planar system formed by 32 carbon atoms saturated with 14 hydrogen atoms in its edge as shown in Figure 1. Distinct functional substituent groups were used to modify the border of this model, such as O-, COO-, OH and COOH, as well their double substitution in the edge of the graphene model (Figure 2). The presence of Ca2+ cation was also included in the models as a first coordination species, and

was found for the coordination of the [Cu(CN)3] 2complex with the graphene model. Figure 4 shows the influence of the Ca2+ cation on the stabilization of the complex formed through molecular orbital analysis. In this figure is possible to note the electronic density formed between the [Cu(CN)3]2complex and the Ca2+ cation. The results obtained by molecular modeling are consistent with the experimental results reported elsewhere (Souza et al., 2013). Both approaches show that the modification in the graphene structure and the presence of Ca2+ cation play an important role in the copper adsorption. It is proposed that the interaction of Ca2+ ions with the

Table 1. Physicochemical properties of the investigated activated carbon samples.

carboxyl or phenol groups on the activated carbon generates an excess of local positive charges, which enhance the adsorption of negatively charged Cu

Sample

SSA (m2 g-1)

AC (%)

DSFG (µeq m-2)

PZC

931

1.2

7.1

is negative. The experimental results also showed

553

5.8

7.4

the charge associated with basic functional groups

849

3.3

7.7

Figure 1. Effects of pH on copper adsorption at 25 ºC. Conditions: [CN]/[Cu] = 4.

66 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

cyanocomplexes, even when the net surface charge

available on the surface of the adsorbent material plays an important role on copper adsorption,

Figure 2. Schematic representation of the graphene model used to adsorb the [Cu(CN)3]2- species and the substitutions made on it.

Figure 3. The most stable complex formed by the adsorption of the [Cu(CN)3]2- species on the modified graphene model assisted by Ca 2+ cation.

copper adsorption only under conditions where the [Cu(CN)3] 2- complex is the predominant species. In conclusion, an adsorption mechanism of copper cyanocomplexes on activated carbon was proposed by an experimental approach that takes into consideration the nature of the interaction among the copper species and the reactive sites of the activated carbon. Differently from the Figure 4. Molecular orbital scheme of the system formed by the coordination of [Cu(CN)3]2- species and the modified grapheme model through Ca 2+ cation.

conclusions of previous works, copper adsorption was mainly ascribed to electrostatic interactions with the adsorbent’s positively charged sites. The interaction of Ca 2+ ions with acid groups

especially at low ionic strength. When these groups

available on the activated carbon generates an

are positively charged, the attraction of negatively

excess of positive surface charges, decreasing

charged copper species is enhanced, whereas under

the net negative charge of carbon particles and,

conditions in which these groups are deprotonated,

therefore, creating favorable sites for adsorption

the metal adsorption decreases significantly.

of the negatively charged cyanocomplexes, even

On the other hand, high ionic strength improves

when the net surface charge is negative.

References Davidson, R. J. (1974) J S Afr Inst Min Metall. 75(4), p. 67–79.

Souza, C.; Majuste, D., Ciminelli, V.S.T. Hydrometallurgy, 2013 (in press).

Fleming, C.A. and Nicol, M.J. (1984). J S Afr Inst Min Metall. 84(4), p. 85–93.

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 2 |

Recovery of Indium and Zinc from Computer Monitors Scrapped by hydrometallurgical techniques A. C. V. Zuccheratte1, C. A. Morais1,*

Centro de Desenvolvimento da Tecnologia Nuclear – CDTN – www.cdtn.br – Belo Horizonte, MG, Brazil Corresponding author: cmorais@cdtn.br - Centro de Desenvolvimento da Tecnologia Nuclear, Campus da Universidade Federal de Minas Gerais - UFMG, MG, Brasil, Av. Antonio Carlos, 6627, CEP 30161-970, Belo Horizonte, MG, Brazil *

Keywords: Indium, zinc, acid digestion, solvent extraction

New technologies are rapidly incorporated

The work was divided into two distinct parts:

to the routine of the society and the existing

(i) dissolution of the metals In and Zn through

technology, though quite new, becomes obsolete.

acid digestion of the sample and (ii) separation of

As a consequence, the out-dated electronics end

the metals through solvent extraction technique.

up in landfills barely adequate to receive such waste. Therefore electronic residues are amongst

Acid digestion

the fastest growing ones in the world and usually In the acid dissolution the influence of the

present a highly toxic character. Computer monitors present as internal coating a compound consisting of oxy-sulfides, which presents a considerable concentration of indium and zinc, in addition to other metals. The recovery of the rare earths (RE) from electronics scraps (e-scraps) and other metals is extremely important as the economic and environmental issues are concerned (Resende and Morais, 2010).

following parameters was investigated: type of reagent, acid/sample ratio, time of reaction and temperature. Following the optimisation of the parameters of the process, dissolution of indium above 98% and of Zinc over 99.5% was achieved. A liquor containing 9.8 g/L of zinc, 1.49 g/L of indium and 102 g/L of sulphate having as impurity 0.016 g/L of iron, in an acidity of 2.2 mol/L H+ was obtained. The most significant

Previous work showed the recovery of the

variables identified in this study were the acid/

metals Eu and Y and most of the zinc present

sample ratio and the temperature. The influences

in the same sample from computer monitors

of these variables are present in Figures 1 and 2.

scrapped. This paper presents the study of the recovery of the metals In and Zn that remained in the sample after the dissolution of Eu and Y.

Solvent extraction

The main constituents of the sample are present

After the acid dissolution, batch experiments of solvent extraction were carried out aiming at

in Table 1.

Table 1. Main constituents of the computer monitor powder after the recovery of Eu and Y.

5.0

0.92

0.38

0.03

1.87

0.72

16.8

10.2

3.19

68 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

Figure 1. Influence of the acid/sample ratio on In and Zn dissolution; T= 200 oC; reaction time: 2h.

Figure 2. Influence of the temperature on In and Zn dissolution. Acid/sample ratio: 1.000 kg/t; reaction time: 2h.

verifying the technical viability and best conditions

with different acids concentrations. The batch

for the separation of the metals to be employed in

experiments indicated that the separation of the

the continuous experiments. In the extraction step

metals In and Zn can be effective using DEHPA 1.0

it was investigated the type of extractant, pH of the

mol/L as extractant, H2SO4 1 mol/L as scrubbing

liquor, and reaction time.

agent and HCl 3 mol/L as stripping agent.

The experiments were carried out at an

The influence of the acidity and the type

aqueous/organic (A/O) volumetric ratio equal to

of extractant are presented in Table 2 and the

1 and concentration of extractant 1.0 mol/L. The

influence of the concentration of sulphuric acid and

extractants investigated were DEHPA (di 2-ethyl

hydrochloric acid are presented in Figures 3 and 4.

hexyl phosphoric acid), IONQUEST 801 (2-ethyl

After the definition of the best conditions

hexyl phosphonic acid mono-2-ethyl hexyl ester)

for the extraction, scrubbing and stripping steps

and CYANEX 272 (Bis-2,4,4-trimethylpentyl-

a continuous experiment was programmed.

phosphinic acid). The extractants investigated

The McCabe-Thiele diagrams indicated that 3

belong to the class of cationic extractants. They

extractions stages and 5 stripping stages was

are able to extract both indium and zinc. The

enough to extract and strip the In from the liquor

selectivity of the indium mainly depends on the

and the loaded organic respectively.

acidity of the liquor, for example, Zn is extracted

Due to the small amount of the liquor, the

at low acidity - pH higher than 1.0, while the In can

continuous experiment contemplated only the

be extracted at a higher acidity (Alamdari, 2004;

extraction and scrubbing steps. The experiment

Tomii et al., 1980; Gouveia and Morais, 2010).

was carried out in mixer-settler cells, with capacity

The stripping experiments were carried out

of 70 mL in the mixer and 250 mL in the settler,

with HCl and H2SO4, at a volumetric ratio of 1

in a counter current system. The stripping step

Table 2. Influence of the extractant and the acidity of the liquor on In and Zn extraction.

Extraction percentage (%)/Separation Factor (FS)

Extractant

DEHPA

IONQUEST 801

CYANEX 272

Acidity

2.2

>3000

2.4

1.0

>3000

>1000

3.9

0.8

>3000

>1000

4.2

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 2 |

Figure 3. Influence of H2SO4 concentration on In and Zn stripping from the loaded DEHPA.

Figure 4. Influence of HCl concentration on In and Zn stripping from the loaded DEHPA.

was carried out in batches simulating the counter current system. The continuous experiment (extraction and scrubbing steps) were carried out with the use of DEHPA 1.0 mol/L as the extractant agent and a solution of H2SO4 1.0 mol/L as the scrubbing agent in order to remove the impurities extracted. Four extraction stages and 4 stages were employed in each step, using a volumetric ratio A/O equal 5 in the extraction and a volumetric ration O/A equal 4 in the scrubbing step. A loaded organic containing 7.5 g/L of In and 0.003 g/L of Zn and a raffinad containing 9.4 g/L

Figure 5. Solvent extraction continuous plant at Center for Development of Nuclear Technology.

Zn and less than 0.001 g/L of In were obtained from a liquor containing 9.8 g/L and 1.49 g/L. The content of the metals in the stripped solution were 26.7 g/L de In e 0.001 g/L de Zn. Figure 5 shows the solvent extraction plant where the continuous experiment was carried out.

Acknowledgements The Authors are grateful to the CDTNâ&#x20AC;&#x2122;s technicians involved with this work.

References ALAMDARI, E. K. Minerals Engineering, 89-92, 2004. RESENDE, L. V.; MORAIS, C. A. Minerals engineering, 277-280, 2010.

70 | ANNUAL ACTIVITY REPORT 2011-2012 â&#x20AC;&#x201D; INCT-ACQUA

TOMII, K., HIDEYUKI, F.; TSUCHIDA, A., 4,292-284, 1980. GOUVEIA, L. R.; MORAIS, C. A. Minerals Engineering, 492-497, 2010.

Acid Rock Drainage: Impacts on the Environment and Metal Recovery

C.A. Carvalho Filho1, D.M. Sales1, P.C.H. Rodrigues1, P. H. Dutra1, C.F. Silva1, V. V. Ferreira1, R.M. Freitas1, T.A. Perilli1, A.C.Q. Ladeira1,* 1 Centro de Desenvolvimento da Tecnologia Nuclear - CDTN , www.cdtn.br, Belo Horizonte, MG, Brazil *Corresponding author: ana.ladeira@cdtn.br - CDTN - Av. Antonio Carlos, 6627, CEP 31270-901, Belo Horizonte, MG, Brazil

Key-words: uranium, radionuclides, manganese, sediment, oxidative precipitation, ion Exchange

Mining industry has a strong potential to

and they were mainly from stations A1-76 and

cause environmental impacts, especially when

A1-1, downstream of the station A1-75 which

the waste rocks and tailings present sulphide

is set in a dam (Figure 3) that collects the acid

minerals. This can be an indicator of one the

water generated in the waste rock pile. The

most detrimental forms of environmental

average concentrations of the radionuclides in

damage: Acid Rock Drainage (ARD). In

sediments (Figure 2) are below the guidelines

Brazil, the acid water generation is caused by

values (LEL Lowest Effect Level) proposed by

the oxidation of pyrite in one uranium site that

Thompson et al., 2005 in a study that assessed

is under decommissioning. A great effort has

the quality of sediments from one region rich in

been made to characterize the influence of the

uranium at Saskatchewan (Canada). However, by

ARD on this site and surroundings as well as to

comparing the values from sediments upstream

determine the extension of the damage and also

and downstream the station A1-75, in the Consult

to find appropriated solutions to be implemented

watershed, it is observed an increase in the

in the closing.

radionuclides concentrations downstream this

The work is divided in two par ts: i) characterization of the site to assess the impacts

station, possibly due to leakage or to unplanned discharges from the dam.

caused by ARD on waters and sediments on the plateau of Poços de Caldas; ii) the recovery of acid mine water.

Recovery of manganese and uranium from the acid water

Impacts Assessment

SO4-2, Al, F-1, U and Mn in concentration around

manganese and uranium that are present in the

The water at pH 3.0 contains mainly Fe, 150mg/L. Mn content is a concern because of

The first part comprises the characterization

the notorious difficulty for its removal at low

of the area depicted in Figure 1. Twelve

pH (Johnson and Hallberg, 2005). The process

sampling stations, located in creeks, rivers, and

of oxidative precipitation with potassium

tailings dams, were used to sample water and

permanganate is an alternative. Sample of the

sediments. The results show that there are high

ARD (figure 3) was chemically characterized

concentrations of metals in water compared

and then was treated by adding KMnO4.

to the Brazilian legislation (COPAM/CERH,

Oxidative precipitation trials were carried

2008). The maximum values found in water

out at pH 3.0, 5.0 and 7.0 in glass beakers

were: 5 Bq/L U; 6.61mg/L Al; 1.81 mg/L Fe;

with 200 mL of liquid samples, under stirring

4.0 mg/L Mn; 1.16 µg/L Cd and 0.8 mg/L Zn.

and at room temperature (25°C± 0.5). The

All these values are above the legislation limits

pH was initially adjusted by adding sodium

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 2 |

Figure 1. Map of the Area showing the Mine (INB - Caldas) with the perimeter of the waste rock pile in green.

Figure 2. Radionuclides average concentrations (N=4) at sampling stations. Horizontal arrows indicate the Lowest Effect Level (LEL) for 238U, 226Ra and 210Pb concentrations in sediments.

hydroxide or sulphuric acid. One aliquot was taken for determining the initial concentration of manganese which varies from 90 to 105 mg/L. Afterward, KMnO4 4% (w/v) was added to the

72 | ANNUAL ACTIVITY REPORT 2011-2012 â&#x20AC;&#x201D; INCT-ACQUA

solutions according to the pre-determined ratio: 1.63 mg KMnO4/mg Mn for experiments at pH 3.0 and 1.54 mg KMnO4/mg Mn for pH 5.0 and 7.0. Samples were collected at pre-established

The precipitates formed were poorly crystalline. Nevertheless it was possible to identify the phases: birnessite (MnO 2 ), hausmanite (Mn 3O 4 ) and manganite (MnOOH) by Raman spectroscopy. The positive results support the potential of oxidative precipitation with KMnO4 for the recovery of Mn as well as the treatment of high manganese content from ARD. Besides Mn, uranium, in concentrations around 11mg/L, was also recovered from the acid water by using ion exchange resins. The recovery of uranium from the acid water has the advantage of generating a product of significant market value, as well as reducing the concentration of this metal in the final effluent to the permissible limits for discharging (Ladeira and Gonçalves, 2007). Strong base anionic resin Amberlite IRA910U and Dowex Figure 3. Acid dam in a forefront and Waste rock pile in the background (INB-Caldas).

MSA were tested in fixed bed column experiments

time, filtered in 0.45µm membrane and analysed by atomic absorption and by X-ray fluorescence spectrophotometry. The results have shown that manganese oxidation by KMnO4 has the advantage of being fast and also feasible at pH near neutrality. At pH 7.0 the process was more efficient and accomplished levels of 99%, meeting the limit set by Brazilian legislation. The concentration of Mn decreases exponentially from around 100 mg/L to concentrations lower than 1.0 mg/L in approximately 10 min of reaction (Figure 4).

were filled with 15mL (1 bed volume) of wet resins.

(ratio high/diameter equal to 4.7). The columns The operation was performed by downstream flow at constant flow rate with a residence time of 6min. The pH of the acid water was around 3. The results are shown in Figure 5. The maximum loading capacity for uranium (Qmax.) presented by the resins Amberlite IRA-910U and Dowex MSA-2 were 98.9 and 108.9 mg.g-1, respectively. It is important to stress that the loading of the resins was hindered by the competitive ions, such as the sulphate in

Figure 4. Effect of pH on manganese removal with KMnO4 from acid effluent. T = 25°C ± 0.5. Dotted line represents the limit for Mn discharge (1.0 mg/L) set by CONANA Resolution 430.

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 2 |

concentration around 1350 mg/L. The uranium in

with ion exchangers, which makes this method

the resins was then eluted using a solution of NaCl

recommended for the acid rock drainage from the

and sulfuric acid (Figure 6).

PoĂ§os de Caldas Plateau.

The percentage of elution was 86.6% and 94.1% for Amberlite IRA-910U and Dowex MSA-2, respectively and the overall recovery was

Acknowledgements

around 96%. According to the results presented here, it can be stated that it is possible to recover the uranium present in the acid mine drainage

Thanks to INB (Industrias Nucleares do Brazil) for the supply of the samples.

Figure 5. Uranium adsorption profile for two different resins. pH = 3.0; flow rate 2,5mL.min-1; temperature 25oC.

Figure 6. Uranium elution profile for different resins. flow rate 2,5mL.min-1; temperature 25oC. NaCl solution 1,5mol.L-1 .

74 | ANNUAL ACTIVITY REPORT 2011-2012 â&#x20AC;&#x201D; INCT-ACQUA

References COPAM/CERH-MG, Deliberação Normativa (DN) Nº 1 de 1º de maio de 2008 - Diário do Executivo – Belo Horizonte - MG, 27, p. 2008. JOHNSON, D.B.; HALLBERG, K.B. Science of the Total Environment 338, 3–14, 2005.

LADEIRA, A.C.Q.; GONÇALVES, C.R. J. Hazard. Mater. 148, 499-504, 2007. THOMPSON, P. A.; KURIAS, J.; MIHOK, S. Environmental Monitoring and Assessment, 110, 71–85, 2005.

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 2 |

research topic 3

Natural and synthetic materials for environmental and technological applications 78

Natural Clay Mineral Nanotubes: Stability, Electronic and Mechanical Properties

Functional material based on modified clay for metal ion speciation and immobilization

Mn3O4 magnetic nanocomposites for dye degradation

science highlights science - ReseARch highlights tOPic 3 |

Natural Clay Mineral Nanotubes: Stability, Electronic and Mechanical Properties Maicon P. Lourenço,1Maurício C. da Silva,1 Luciana Guimarães,2 Hélio A. Duarte*1 1 Grupo de Pesquisa em Química Inorgânica Teórica – Department of Chemistry – Universidade Federal de Minas Gerais (UFMG) – Belo Horizonte, Brazil 2 Department of Natural Science – Universidade Federal de São João Del Rei (UFSJ) – São João Del Rei, MG, Brazil *Corresponding author: duarteh@ufmg.br, Department of Chemistry, Universidade Federal de Minas Gerais, Av. Antonio Carlos, 6627, CEP 30270-091, Belo Horizonte – MG, Brazil.

Keywords: Imogolite, Halloysite, Chrysotile, SCC-DFTB

Clay mineral nanotubes (NTs) are naturally occurring materials, which present well defined structural parameters. These compounds are very attractive for developing new advanced materials with enhanced properties. They are very versatile, easily synthesized and functionalized. Therefore, clay mineral NTs are interesting target materials to be used as support for catalysis, ionic channels, molecular sieving, component of hybrid materials, gas storage and other applications in nanotechnology. Imogolite, halloysite, and chrysotile are examples of clay minerals NTs (Fig. 1). Imogolite is composed of single walled NTs, monodisperse and has always the same size and quirality. Its chemical composition is (HO)3Al2O3SiOH. The tube walls consist of a curved gibbsite-like sheet (Al(OH)3), where the inner hydroxyl surface of the gibbsite is replaced by (SiO3)OH groups. Halloysite is polydisperse with stoichiometry Al2Si2O5(OH) 4.nH2O that can grow into long tubules and is chemically similar to kaolinite. It consists of a gibbsite octahedral sheet (Al(OH)3), which is modified by siloxane groups at the outer surface. The chrysotile structure is composed of brucite (Mg(OH)2) and tridymite (silicon dioxide, SiO2) layers. The brucite octahedral sheet forms the outer side of the tube and SiO 4 groups

Recently, we have applied self-consistent-charge density-functional tight-binding (SCC-DFTB) method (Oliveira et al. 2009) to investigate the stability, the electronic and the mechanical properties of the clay mineral NTs. The strain energy, defined as the energy involved in rolling a layer into a nanotube, has been calculated for the imogolite, halloysite and chrysotile NTs. Figure 2 shows the strain energy curve as a function of NTs radii. The imogolite strain energy curve presents a minimum around 10 Å. The zigzag (12,0) symmetry is the most stable NT while the armchair structures, not detected in experiments, are less stable than zigzag ones (Guimarães et al., 2007). In contrast to imogolite, halloysite and chrysotile NTs do not present a minimum in the strain energy curve (Guimarães et al., 2010, Lourenço et al., 2012) which decreases with the increasing of the tube radius (R) and converges approximately as R–2. In fact, with the exception of the imogolite, inorganic and carbon nanotubes follow the same trend. The Young’s moduli of clay mineral NTs have been estimated numerically using the equation:

1  ∂2 E  Vo  ∂ε 2 

ε =0

are anchored to the inner side. Its chemical

where Vo is the equilibrium volume, ε is the strain

composition is Mg3Si2O5(OH) 4.

and E the total energy.

78 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

Figure 1. (a) Imogolite, (b) halloysite and (c) chrysotile structures.

Figure 2. Strain energy as a function of tube radius for (n,0) zigzag and (n,n) armchair single walled NTs.

Table 1. Estimated band gap energy gap and Youngâ&#x20AC;&#x2122;s moduli of imogolite, halloysite and chrysotile.

Nanotube Symmetry Imogolite

Halloysite

Chrysotile

Gap / eV

Y / GPa

(10,0)

10.3

196

(12,0)

10.3

242

(7,7)

10.6

368

(8,8)

10.6

329

(16,0)

7.7

273

(17,0)

7.9

264

(14,14)

9.3

302

(15,15)

9.4

301

(14,0)

10.0

272

(24,0)

10.0

273

(19,19)

10.1

282

(20,20)

10.1

319

The estimated Youngâ&#x20AC;&#x2122;s moduli of some selected imogolite, halloysite and chrysotile structures are shown at Table 1. The estimated values are in the range of 175 and 300 GPa, which are comparable to those of inorganic nanotubes such as MoS2 (230 GPa) and GaS (270 GPa). As can be seen in Table 1, the SCC-DFTB estimates of the band gap energy indicate that the clay mineral nanotubes are insulators with high band gap values. The electrostatic field has been calculated using the atomic charges obtained from the SCC-DFTB method. The inner wall of imogolite and chrysotile NTs is mainly negative while the outer wall is slightly positive. For halloysite, the inner wall is mainly positively charged, while the outer surface has a weakly negative charge, as it is expected. In general, the clay mineral NTs are insulator and the stiffness of the NT is similar to other inorganic NTs and comparable to steel.

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 3 |

We have proposed a molecular modeling

or to modify it through dehydroxylation (Kang, et al.

approach and investigated the formation mechanism

2011). SCC-DFTB calculations are being carried

of the clay mineral NTs. The minima observed in

out in our laboratory to investigate the stability and

the strain energy curve of the imogolite explain

the electronic and mechanical properties of such

why imogolite is monodisperse with well-defined

modified nanotubes. The clay mineral nanotubes

structural parameters such as chirality and diameter. The hydrogen-bond network inside the NTs contributes to its stabilization, but it is not responsible for the NT formation. In fact, the hydroxyls inside of the NT contribute to make the imogolite a good ion conductor. Recently, the inner side of the imogolite has been successfully modified to incorporate organic groups

are promising materials for heavy metal retention, nanoreactors and as structural component for new organic-inorganic polymer composites.

Acknowledgments The European Commission FP7 Marie Curie TEMM1P PIRSES-GA-2011-295172 is also gratefully acknowledged.

References OLIVEIRA, A.F.; SEIFERT, G.; HEINE, T.; DUARTE, H.A. Density-functional based tight-binding: An approximate DFT method. Journal of the Brazilian Chemical Society, 20, 1193-1205, 2009. GUIMARAES, L., ENYASHIN, A.N., FREN ZEL, J., HEINE, T., DUARTE, H.A.; SEIFERT, G. Imogolite nanotubes: Stability, electronic, and mechanical properties. ACS Nano, 1, 362-368, 2007. GUIMARAES, L., ENYASHIN, A.N., SEIFERT, G.; DUA RT E, H. A . S tructural, electronic, and mechanical properties of single-walled halloysite nanotube models. Journal of Physical Chemistry C, 114, 11358-11363, 2010.

80 | ANNUAL ACTIVITY REPORT 2011-2012 â&#x20AC;&#x201D; INCT-ACQUA

LOURENĂ&#x2021;O, M. P.; OLIVEIRA, C. D.; OLIVEIRA, A. F.; DUARTE, H. A.; Structural, Electronic and Mechanical Properties of Single-Walled Chrysotile nanotube Models. Journal of Physical Chemistry C, 116, 9405, 2012. K ANG, D.Y.; Z ANG, J.; JONES, C.W.; NAIR, S. Single-walled aluminosilicate nanotubes with organic-modified interiors. Journal of Physical Chemistry C, 115, 7676-7685, 2011.

Functional material based on modified clay for metal ion speciation and immobilization

A. M. Ferreira1*, V. S. T. Ciminelli2, W. L. Vasconcelos2 1 Centro Federal de Educação Tecnológica de Minas Gerais - CEFET – Department of Chemistry, Belo Horizonte, MG, Brazil 2 Escola de Engenharia – Department of Metallurgical and Materials Engineering, Universidade Federal de Minas Gerais - UFMG, Belo Horizonte, MG, Brazil *Corresponding author: angelamello@des.cefet-mg.br - Av. Amazonas 5253, CEP 30.480-000, Belo Horizonte, MG, Brazil

Key-words: clay mineral, functionalization, adsorption

Many efforts have recently been devoted to

The intercalation of organic species within the

the design and preparation of novel functional

spaces between interlayers of inorganic layered

materials based on modified clay minerals for

crystals provides nanostructures consisting

adsorption of organic and inorganic pollutants

of alternating layers of inorganic and organic

(Guimarães et al., 2009; Paul et al., 2011). The

compound.

smectite clay present a 2:1 structure and, among

The intercalation reactions occur by insertion

the mineral clays of this group, montmorillonite

of mobile guest species (neutral, molecules, or

and hectorite have been the most commonly

ions) into the accessible crystallographic-defined

used clays to investigate the functionalization

vacant sites located between the layers (interlayer

processes due to their availability and adequate

spacing) of the layered host structure (Wypych

characteristics of expandability (Prado et al.,

and Satyanarayana, 2004). Modification with

2005). The 2:1 type layered silicates present

organosilane involves grafting reactions by

a “sandwiched” structure; i.e., one Al(Mg)–

establishing covalent bonds between the reactive

O4 (OH)2 octahedral sheet bound to two Si–O

groups of the layer, normally hydroxyl groups,

tetrahedral sheets, as shown in Figure 1. .Surface

and silane molecules. These reactions can be

modification is a key step concerning the

restricted to the external surface (the basal

application of clays for selective immobilization

spacing remains unchanged) or to the interlayer

of pollutants. Taylor-made Hybrid Material based

surface, in which case an interlayer expansion

on modified clay with functional groups, such

occurs. The resulting material can be defined

as amino, thiol, vinyl, long carbon chain have

as hybrid materials, or more specifically,

been studied for new applications such supports

surface–modified inorganic layered materials

for catalysts, sorbents for pollutants and the

(Wypych and Satyanarayana, 2004).

manufacture of modified electrodes for (bio)

This work was focused on the functionalization

electrochemical applications (Guimarães et al,

of natural clay with thiol groups by grafting of

2007).

3-mercaptopropyltrimethoxysilane. We report

Organosilanes have been employed for

here the possibility of utilizing the Brazilian

modifications of layered silicates, with natural

smectite clay for the preparation of an organic-

smectites being the most commonly tested clays

inorganic hybrid material. The thiol group was

in functionalization processes (Shen et al., 2007).

chosen due its great affinity for some toxic

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 3 |

species as Cd2+, Hg2+, Zn2+, Cu2+, Ag+ and As(III).

hydrophobic. X-ray diffraction results indicated

Samples were modified by acid treatment followed

that their original structure had been preserved and

by immobilization of ligands containing thiol

there was a clear increase in the average interlayer

(-SH) groups by covalent grafting with surface

spacing (12 Å to 16.0 Å) after functionalization due

and interlayer silanol groups. The modification

to intercalation of organosilane (Figure 3).

was carried out under anhydrous conditions with (3-mercaptopropyl) trimethoxysilane (Figure 2).

Adsorption experiments have been performed to highlight the possible use of the grafted smectite

The functionalization process changed the

for metal ions removal from dilute solutions.

hydrophilic nature of the clay mineral into

The amount of immobilized and available thiol group has been determined by using the Ag+ ions standard test. It was found 1.16 meqSH/g of clay,

Adsorption experiments demonstrated the strong affinity of this thiol modified clay by As(III). The highest loading capacity (22.3 mg/g) and the

Figure 1. (a) Idealized structure of 2:1 type layered silicate. (Top: stick and ball style; bottom: polyhedron style.).(b) MEV micrographs of smectite clay.

Figure 3. DRX pattern of natural and modified clay.

82 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

Figure 2. Schematic illustration: functionalization process.of the direct hydrolysis and condensation reaction between hydrolyzable alkoxy group of (3-mercaptopropyl)trimethoxysilane and clay surface hydroxyl grpups.

maximum arsenic speciation occurred at pH5,

cadmium uptake observed for all the tests using the

where the trivalent species are present in its neutral

modified clay. The affinity of the SH-modified clay

form, H3AsO3. The thiol-functionalized smectite

towards Cd(II) ions can be explained by the Lewis

presented binding capacity of Ag+ ions about ten times higher compared to the ungrafted sample. These results support a mechanism of adsorption involving primarily ion complexation by the

acid–base theory. The Cd(II) is a soft Lewis acid, thus it should bind strongly to thiol groups, which is a soft Lewis base. The formation of CdS bonds

thiol groups (specific) instead of cation exchange

is expected to significantly improve the stability of

(unspecific) (Figure 4).

the pollutant. This new hybrid organic-inorganic

The accessibility to the reactive centers was 60-75%. . Regarding Cadmium ion uptake capacity , it was found 44 mg/g (0.41 mmol/g) and 17 mg/g (0.15 mmol/g) for the functionalized and natural clay, respectively, at pH 6 (160% higher). ). For the functionalized clay, a proposed mechanism

material may be a good alternative for separation and pre-concentration of metal ions. The results obtained in the present work showed that the thiol functionalized clay is an effective sorbent for selective As(III), Cd(II) and Ag ion

involves the complexation of the ion Cd (II) by

immobilization. Thus, the adsorption capacity of

the thiol (-SH) group and the release of H+ ions to

smectites can be enhanced by surface modification

solution as shown in the equation (1):

using organo-functional silane coupling agents. (1)

This new hybrid organic-inorganic material

Evidence for the mechanism described above

may be a good alternative for separation and

Cd2+ + 2R-SH

R-S-Cd-S-R + 2H+

is includes the reduction of pH values during

pre-concentration of metal ions.

Figure 4. DRIFT of the thiol modified clay, before (BHSH) and after silver ion adsorption (BHSH-Ag).

References G U I M A R Ã ES, A . M. F.; C I M I N EL L I, V. S. T.; VASCONCELOS, W. L. Applied Clay Science 42, 410-414, 2009.

SHEN, W.; HE, H.; ZHU, J.; YUANA, P.; FROST, R. L. Journal of Colloid and Interface Science 313, 268-273, 2007.

PAUL, B. ; MARTENS, W. N.; FROST, R. L. Applied Surface Science 257, 5552–5558, 2011.

WYPYCH, F.; SATYANARAYANA, K. G. Clay Surface: Fundamentals and applications. Interface Science and Technology. First edition. Amsterdam, London,Tokyo, New York: Elsevier Academic Press. Vol. 1, p. 2 - 56, 2004.

PRADO, L. A. S.; KARTHIKEYAN, A. C. S.; SCHULTE, K.; NUNES, S. P. ; TORRIANI, I. L. Journal of NonCrystalline Solids 351, 970-975, 2005. GUIMARÃES, M. F.; CIMINELLI, V. S. T.; VASCONCELOS, W. L. Journal Materials Research 10, 37-41, 2007.

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 3 |

Mn3O4 magnetic nanocomposites for dye degradation G. C. Silva1,*, A. M. Ferreira2, V. S. T. Ciminelli1 1 Escola de Engenharia, Departamento de Engenharia Metalúrgica e de Materiais, Universidade Federal de Minas Gerais - UFMG, Belo Horizonte, MG, Brazil 2 Centro Federal de Educação Tecnológica de Minas Gerais, Departamento de Química, Belo Horizonte, MG, Brazil *Corresponding author: angelamello@des.cefet-mg.br - Av. Amazonas 5253, CEP 30480-000, Belo Horizonte, MG, Brazil

Key-words: magnetic composite, manganese oxide, dye degradation

Treating of dye effluents prior to their

to the surface bound Mn3+/Mn4+, followed by

discharge is essential, since the presence of dyes

release of organic oxidation products and Mn2+

in water reduces light penetration hindering

arising from reductive dissolution of Mn oxides

photosynthesis in aquatic plants apart from

(Chowdhury et al., 2009; Zaied et al., 2011).

the undesirable coloring of streams. Mn3+ and

Zaied et al. (2011) have used thin layers of

Mn4+oxides and hydroxides are powerful oxidants

birnessite (manganese dioxide) to degrade MB

due to their high reducing potential and can oxidize many inorganic and organic compounds (Silva et al., 2012, 2013; Rhadfia et al., 2010). In view of its strong oxidative characteristic, Mn3O4

contained in aqueous solutions and revealed the presence of intermediate reaction products (azure A (AA), azure B (AB), azure C (AC), and

has been evaluated as an effective oxidant for the degradation of dyes in water (Chowdhury et al., 2009; Zaied et al., 2011). The introduction of magnetic properties in Mn3O4 can improve its separation from dye effluents. Here, we report the application of a magnetic composite based on Mn3O4 synthesized at room temperature and by using air as an oxidant in the dye methylene blue (MB) degradation. Decolorization of the dye MB by Mn 3O 4 magnetic composites (Mnmag) was investigated spectroscopically through UV–visible (UV-vis) spectroscopy and the discoloration efficiency (%) of the samples at different times of reaction was calculated. According to the literature, it has been well established that oxidative degradation of organic matter by Mn oxides proceeds via a surface mechanism, that is, the organic compound is adsorbed on surface of Mn oxides to form a surface precursor complex, electron transfer then occurs within the surface from organic reductant

84 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

Figure 1. UV-vis spectra peak fitting of 1.4 x 10 -5 mol.L-1 MB solution before and after charging Mnmag suspensions at pH 3.0.

thionin (Th) during interaction. The characteristic

of color disappeared after 60min and remained

UV-vis λmax of AA, AB, AC, and Th were

constant until 180min. The results show that at pH

identified as 628, 638, 618 and 601 nm, respectively

4.0 and pH 6.0, MB was not oxidized by Mn3O4,

(Zaied et al., 2011).

indicating that the role of acid is very important in -5

-1

UV-vis spectra of the 1.4 × 10 mol.L MB solution before and after charging Mnmag −1

suspensions (1.4 g.L ) at pH 3.0 are shown in Figure 1.

the decolorization reaction, what is explained by the H+ dependent Mn3O4 reductive reaction. Methanol (MeOH) was used to dissolve organic compounds present onto the solids after

Spectra of dye solution, before adding the solids,

interaction in the aim to identify them. The solids

clearly exhibit the characteristic λmax (maximum

were immersed during 24h. The identification

wavelength) peak of MB at 667nm. As soon as the

of the organic compounds was made by UV–vis

solids are added in the dye solution at pH 3.0, the

spectroscopy. The measured value of λmax= 600nm

peaks changed position and intensity indicating

is the characteristic λmax of thionin (Zaied et al.,

that MB was oxidized by Mn3O4. MB is oxidized to AB after 10min and to Th after 60min. Figure 2 shows the discoloration efficiency (%) versus time for Mnmag suspensions at pH 3.0. 85%

2011), indicating that the MB fully demethylated derivative is the adsorbed organic compound after MB oxidation. The pH of the decolorization medium exerts significant effect on the degree of dye decolorization. At lower pH, the Mn 3O 4 nanoparticles show superior capacity of decolorization; the degrees of decolorization of MB in acidic media reached 85% within 60min Therefore, the design and development of nanostructured composites with magnetic properties are usable for functional decomposition/removal and immobilization of contaminants from water. Another important aspect is the advantage of magnetic property which

Figure 2. Discoloration efficiency (%) versus time of 1.4x10 -5 mol L-1 MB solution in interaction with 1.4 g.L-1 Mnmag suspensions at pH 3.0.

facilitates the process of solid/liquid separation avoiding filtration and being suitable for treating large volumes.

References CHOWDHURY, A.N.; AZAM, M.D.S.; AKTARUZZAMAN, M.D.; RAHIM, A. 2009. J. Hazard. Mat., 172, 1229–1235. SILVA, G.C.; ALMEIDA, F.S.; DANTAS, M.S.S.; FERREIRA, A.M.; CIMINELLI, V.S.T. 2013. Spectroch. Acta. Part A, 100, 161-165.

RHADFIA, T.; PIQUEMAL, J.Y.; SICARD, L.; HERBST, F.; BRIOT, E.; BENEDETTI, M. 2010. Appl. Catal. A. Z A I E D, M .; P EU LO N A , S .; B E L L A K H A L , N .; DESMAZIÈRESD, B.; CHAUSSÉA, A. 2011. Appl. Catal. B, 101, 441–450.

SILVA, G.C.; ALMEIDA, F.S.; FERREIR A, A.M.; CIMINELLI, V.S.T. 2012. Mat. Research, 15, 403-408.

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 3 |

research topic 4

Acid rock drainage 88

Comparison between two sequential extraction procedures to assess Arsenic mobility

Precipitation of Al-Fe (hydr)oxides to treat water contaminated with Arsenic

Removal of manganese from Acid Rock Drainage using bone char as adsorbent â&#x20AC;&#x201C; Columns experiments

science highlights science - ReseARch highlights tOPic 4 |

Comparison between two sequential extraction procedures to assess Arsenic mobility Renato W. Veloso1*, Susan Glasauer2, Jaime W. V.de Mello1, Luísa P. Cardoso1 Department of Soils, Federal University of Viçosa, Viçosa, MG, Brazil School of Environmental Sciences, University of Guelph, Guelph, ON, Canada *Corresponding author: rwveloso@gmail.com - University of Viçosa, Av. P.H. Rolfs, CEP 36570-000, Viçosa, MG, Brazil 1 2

Key-words: Acid Rock Drainage, Arsenic, extraction methods

Arsenic is a common contaminant in mining environments impacted by Acid Rock Drainage (ARD). The process is initiated by the oxidation of sulphide-bearing materials exposed to surface conditions and induces the acidification of drainage waters that may increase metal and metalloid mobility, including arsenic. The As content of drainage waters will be affected by several factors, including the As chemical species, Fe content and pH. Risk is, however, commonly assessed by determining total As content in the associated solid substrate. This approach recognizes that the solid phase forms the largest reservoir of As in typical natural systems. Understanding the chemical form of As in the solid phase is vital to evaluate how reactive As may be remobilized from soils and sediments. Sequential extraction procedures are developed in order to obtain a more precise understanding of As mobility than single extraction. The aim of our research was to test two different sequential extraction for As. Samples of sediments were collected within a gold mining area impacted by AMD, located in Minas Gerais State, Brazil. Four samples were collected from two creeks. One sample was from near the source spring and the other from downstream for each creek. Two sequential extraction methods were performed. The first sequential method, SE.1, described by Keon et al. (2001) was slightly altered. The extraction of As-linked to sulfides was not performed. The extraction of As associated to well-crystalline Fe and Al (hydr)oxides was replaced by the method developed by Wenzel et al. (2001). The

88 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

extraction of As linked to organic matter was added, according to the method described by Tessier et al. (1979). Finally, the final extraction step (silicates) was substituted by acid digestion of the remaining solids after freeze drying. The second sequential method, SE.2 was described by Huang and Kretzschmar (2010). The only alteration was to replace the extraction step of As bound to organic matter by the extraction developed by Tessier et al. (1979). The total As content of the samples was determined by digestion with inorganic acids (HF, HNO3 and HF). The external standard (SRM 2710a) was treated by the same procedures. The remaining As after shaking the samples in a 60 mg L -1 As solution for 1 h was analyzed to assess the As adsorption capacity of these sediments. The As concentrations were measured using graphite furnace atomic absorption spectroscopy (GFAAS, Perkin-Elmer 4100ZL). Results for the external standard yielded recovery rates between 90 and 107 %. The source water springs for both creeks (DC.1 and RC.1) had the highest As contents, 4792 and 3851 mg.kg-1, respectively. The As contents for the downstream samples (DC.2 and RC.2) were lower, at 1153 and 1092 mg.kg-1, respectively. The As content was related to the distance from the As source, since the springs are closer to sites of active mining. The remaining As values were lower for the water springs, having presented values lower than the detection limit, and slightly higher for the downstream samples, 14.3 and 10.8 mg.L-1, for DC.2 and RC.2, respectively. The values indicate a high As adsorption capacity,

which could explain the high As content of sediments from springs. The sequential extraction results were similar with respect to predicting As mobility. The samples from the source springs, DR.1 and RC.1, showed that most As was exchangeable and associated with the poorly crystalline (hydr)oxides fractions, with the sum of these fractions higher than 88 e 68 % of the total As extracted by SE.1 and SE.2, respectively. On the other hand, downstream samples showed As primarily associated with the more insoluble fractions, with higher than 71 and 55 % by SE.1 and SE.2, respectively. Most As was associated with the well-crystalline fraction (Figure 1). The largest discrepancies between the two methods were observed for the exchangeable fraction. The As extraction by 1 mol.L-1 of phosphate in SE.1 mobilized more As than did 0.1 mol.L-1 phosphate for the same step in SEM.2, as expected. The higher concentration of phosphate likely released more As from Fe and Al hydr(oxides) (Fig.1), Consequently, this extraction likely overestimated the as mobility. Another important observation was that the final

extraction step for the SE.2 procedure did not dissolve all Fe and Al (hydr)oxides, because the remaining solid had a yellowish tinge for both downstream samples. This probably explains why the As extracted in the residual fraction was higher using method SE.2 than SE.1. Finally, the lower As content associated to sulfides in SE.2 suggest the absence of this mineral phase; so, it is likely that this step released part of the As linked with well-crystalline (hydr)oxides in SE.1. The As content in the sediments and its availability was associated with the proximity to the mining activity and the output of AMD in two creeks. The methods tested indicated that the As in the sediments close to the source was associated with the more mobile fractions, while the As in downstream samples was linked to more refractory fractions. The sediments overall showed a high As adsorption capacity. The extraction methods showed important differences in assessing both the most labile fraction (P-extractable) and the most refractory fractions.

Figure 1. Percentage of As in different sediment fractions assessed by two sequential extraction procedures, SE.1 and SE.2.

References Huang and Kretzschmar, Anal. Chem., 82 (13) 5534, 2010.

Tessier, A.; Campbell, P.G.C.; Bisson, M. Analytical Chemistry 51: 844-851, 1979.

Keon N. E.; Swartz C. H.; Brabander D. J.; Harvey C., Hemond H. F. Environ Sci Technol 35, 2778â&#x20AC;&#x201C;2784, 2001.

Wenzel, W.W.; Kirchbaumer, N.; Prohaska, T.; Stingeder, G.; Lombi E.; and Adriano, D.C. Anal. Chim. Acta, 436, 1â&#x20AC;&#x201C;15, 2001.

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 4 |

Precipitation of Al-Fe (hydr)oxides to treat water contaminated with Arsenic Jaime W. V. de Mello1*, Massimo Gasparon2, Juscimar da Silva3 Department of Soils, Federal University of Viçosa, Viçosa, MG, Brazil School of Earth Sciences, The University of Queensland, Brisbane-QLD, Australia 3 EMBRAPA Vegetables, Brasília/Anápolis, Federal District, Brazil *Corresponding author: jwvmello@ufv.br - Department of Soils, Federal University of Viçosa, Av. P.H. Rolfs, CEP 36570-000, Viçosa, MG, Brazil 1 2

Key-words: Arsenic, geochemical barrier, Al-Fe (hydr)oxides

One of the most critical and challenging

may be advantageous. It is well known that Al

problems faced by mining industry is the

hydroxides are less efficient than Fe (hydr)oxides

treatment of waste water. Mine eff luents

in retaining inorganic pollutants. Nevertheless,

generated during the base metal processing may

Al substituting Fe enhances the redox stability

present high concentration of trace elements

and the adsorption capacity of Fe (hydr)oxides.

including arsenic (As). In areas where the

Therefore, the purpose of this work was to

generation of acid rock drainage (ARD) is

co-precipitate Al-Fe (hydr)oxides in the presence

observed that problem is even more critical, as

of As.

sulphide-bearing ores are oxidized when exposed

Al-Fe (hydr) oxides were synthesized

to atmospheric conditions, producing acid waters

following Schwertmann and Cornell (2000)

with high polluting potential.

report, but the As was added together with

Processes involving precipitation of Fe and

Fe and Al salts, before precipitation of Al-Fe

Al (hydr)oxides have been widely studied as a

(hydr)oxides. Therefore, it was assessed As

mean to remove As from wastewaters. Hence,

co-precipitation, and not only adsorption. It was

water treatment by precipitating Al and Fe

synthesized different Fe-Al (hydr)oxides from

hydroxide phases in AMD water environments

ferrous and Al salts, in three different Fe:Al

Table 1. Concentration of As in supernatant solutions in equilibrium with precipitates at different aging periods. (As detected by AFS1)

Fe:Al Ratio

Initial As (mg/L)

24h

7º Day

1:0.7

5.0

45.94 (7.81)

36.48 (5.16)

1:0.3

5.0

88.27 (2.93)

1:0.0

5.0

1:0.7

14º day

21º day

90º day

<DL

0.92 (0.33)

<DL

1.66 (0.38)

11.61 (4.63)

<DL

6.05 (0.83)

<DL

1.0

6.52 (0.45)

12.52 (2.37)

1.65 (0.76)

<DL

1:0.3

1.0

12.03 (4.77)

0.48 (0.16)

0.97 (0.27)

<DL

1:0.0

1.0

<DL

1:0.7

0.2

1.27 (0.37)

0.97 (0.10)

<DL

1:0.3

0.2

3.10 (1.06)

<DL

1:0.0

0.2

<DL

ug/L 2

DL = 0,50 ug/L; 2Standard deviations.

90 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

ratio (1:0.7; 1:0.3; 1:0). Two different experiments

the lower initial As concentration (200 µgL-1) that

were performed: one with sulphates and other

limit was attained in only 24 hours, but at higher

with chlorides. A 10,000 mg L Merck standard

initial concentrations of As (5,000 µgL-1) it was

solution was added to deionized water in order to

necessary more than a week to reach that threshold

obtain three different concentrations of As (5.0;

for treatments containing more Al. On the other

1.0; 0.2 mg L-1). Then the ferrous and Al salts were

hand, the As concentrations dropped below the

added to the solutions

detection limit in the treatments containing only

-1

in order to obtain the different Fe:Al molar

Fe as fast as 24 h, independent on the initial As

ratios. Precipitation was achieved by adding 5 M

concentration. These results agree with previous

KOH solution to pH 11.7 and the suspensions were

findings showing that Al is less effective than Fe

aged during 3-4 months. Slow oxidation of Fe and

to treat As contaminated water.

incorporation of Al3+ in the goethite structure were

In spite of higher detection limit, results for

achieved by daily stirring the suspensions during

chlorides showed the same trend as verified to

some minutes. All experiments were conducted

sulphates. There was a drastic drop in the soluble

in duplicate.

As in equilibrium with precipitates. Independent

Soluble As in equilibrium with precipitates,

on the Fe:Al ratio the soluble As was decreased to

obtained from sulphates salts of Fe and Al,

less than the detection limit, but in this experiment

drastically dropped in the first day after

it took more than 1 month (Table 2).

precipitation (Table 1). All treatments were

Fe-Al (hydr)oxides precipitation was efficient

effective to remove arsenic from water, as the

to clean up the water contaminated with As, but

concentrations decreased to less than the World

the lower the Al content the faster was the WHO

Health Organization (WHO) recommended limit

threshold attained The threshold for clean up the

for drinking water and even bellow the detection

As contaminated water was attained faster when

limit. The lower the initial concentration of As,

sulphates salts were used to precipitate the Al-Fe

the faster was the WHO threshold attained. To

hydroxides.

Table 2. Concentration of As in supernatant solutions in equilibrium with precipitates during the aging period. (As detected by ICP-OES1)

Fe:Al Ratio

Initial As (mg/L)

03 h

24 h

15º day

1:0.7

5.0

52.4 (11.4)

45.4 (3.4)

1:0.3

5.0

<DL

37.8 (19.4)

<DL

1:0.0

5.0

<DL

1:0.7

1.0

28.2 (9.0)

1:0.3

1.0

1:0.0

30º day

60º day

120º day

<DL

37.8 (5.2)

<DL

25.6 (0.8)

<DL

1.0

<DL

1:0.7

0.2

<DL

1:0.3

0.2

<DL

1:0.0

0.2

<DL

ug/L 2

71.4 (52.6) 111.4 (58.2)

DL = 11,6 ug/L; 2Standard deviations.

References Schwertmann, U. and Cornell, R.M. Wiley-VCH, Weinheim ; Chichester. :727-738, 2000.

SCIENCE HIGHLIGHTS - RESEARCH TOPIC 4 |

Removal of manganese from Acid Rock Drainage using bone char as adsorbent – Columns experiments D. C. Sicupira,1 A. C. Q. Ladeira,2 M. B. Mansur1* 1 Departamento de Engenharia Metalúrgica e de Materiais, Universidade Federal de Minas Gerais - UFMG, Belo Horizonte, MG, Brazil 2 Centro de Desenvolvimento da Tecnologia Nuclear - CDTN, Belo Horizonte, MG, Brazil * Corresponding author: marcelo.mansur@demet.ufmg.br – Departmento de Engenharia Metalúrgica e de Materiais, Universidade Federal de Minas Gerais, Av. Antonio Carlos, 6627, Belo Horizonte, MG, Brazil

Key-words: Manganese, Bone char, Adsorption

Acid Rock Drainage (ARD) has been identified in the mining region of Caldas municipality, Minas Gerais, Brazil. The drainage generated in this region contains radionuclides (U, Th, among others) as well as species of Mn, Zn, Fe, and Fions at concentration levels above those permitted by Brazilian law regarding their direct discharge into the environment. The current treatment of such acidic waters consists of metals precipitation with lime, followed by pH correction. Most metal species are precipitated, but the removal of manganese ions from ARD is notoriously difficult due to their complex chemistry (Bamforth et al., 2006; Robinson-Lora and Brennan, 2010). For a complete precipitation of manganese, the pH must be raised to around 11, and such an operation involves a significant consumption of lime (Ladeira and Gonçalves, 2007). In addition, after the manganese has been removed, the pH must be neutralized for discharge. Therefore, it is costly, generates large volumes of sludges, and requires the consumption of high quantities of reagents to be effective. A promising method based on the removal of manganese using bone char as an adsorbent was recently proposed (Sicupira et al., in press). Manganese was quantitatively removed from ARD at pH values of near 6 to 7. One advantage is that no pH correction of the treated effluent is necessary due to the buffer effect of the bone char. Previous batch equilibrium and kinetics-batch tests revealed that the adsorption of manganese when using bone char was influenced by the solid/liquid ratio. The particle size and temperature studied produced almost no effect on the manganese adsorption within the evaluated

92 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

operating range. The maximum adsorption capacity (qm) found for manganese, based on the Langmuir model, was 22 mg g-1. In this study, continuous fixed bed column experiments were conducted to determine the adsorption capacity of bone char under continuous flow rate. Runs were performed in down flow mode and at room temperature. The column was filled with 40 g of bone char with a particle size of 417-833 µm. The effluent (pHi = 2.96 or 5.50) was continuously fed into the column using a peristaltic pump. The range of initial pH was chosen based on previous batch equilibrium and kinetics-batch studies, and the ARD effluent sample presented a typical pH value of approximately 3. The diameter of the column’s adsorptive bed was 2.2 cm, and a hydraulic flow rate of 7.5 mL min-1 was maintained constant. Effluent samples were collected from the column at determined periods, filtered and acidified using HNO3 before being analyzed by ICP-AES. The bone char used in this study was supplied by Bone Char do Brasil Ltda (Maringá, Brazil) and basically contained hydroxylapatite Ca10 (PO4) 6(OH)2 and calcite CaCO3. The main characteristics of the used bone char are as follows: real density = 2.9 g cm-3, total pore volume = 0.275 cm3 g-1, surface area = 93 m2 g-1, and particle size = 417-833 µm. The ARD effluent was collected in an area near the closed uranium mine in the city Caldas, Brazil. Its metal original composition as well as the composition after ph adjustment is shown in Table 1, which includes the limit concentration for discharge in Brazil according to CONAMA (2005).

The effect of the initial pH of the ARD effluents is shown in Fig 1. The increase in the initial pH from 2.96 to 5.50, showed that the saturation point is quickly reached for the pHi = 2.96. The saturation point occurred after 240 min for pHi = 2.96 and after 660 min for pHi = 5.50. In fact, increasing the initial pH from 2.96 to 5.50, at a constant flow rate, the breakthrough time was extended from 360 min to 720 min, and the number of BVb was extended from 35.1 to 70.2. The ARD effluent, at pHi = 2.96, contains other metal ions within the solution that compete with manganese for binding

Figure 1. Effect of the initial pH on the Mn removal with bone char in fixed bed column (Flow rate = 3.0 mL min-1, mass = 20 g, 417-833 µm, continuous curves from the Thomas model).

sites. This can occur either through the competition of the other metal ions with manganese or through the formation of the precipitate of these metal ions on the bone char surface, which can block the binding sites. As no prior study could be found in the literature using bone char as an adsorbent for the removal of manganese in fixed bed columns, no comparison of the results obtained in this study was possible. The maximum manganese loading calculated in continuous tests using bone char was 6.03 mg.g-1. As new solutions are constantly fed into the column, the calcite present in the bone char is rapidly consumed. This action made the pH value of the effluent leaving the column drop from approximately 8.0 to 2.96 in only a few minutes. Another fact that can also prevent the manganese removal from fixed beds is the high concentration of calcium in the effluent. The manganese removal mechanism is based on the ion exchange with the calcium present in the hydroxyapatite structure; therefore, high concentrations of calcium in the effluent may negatively affect the ion exchange of calcium with manganese.

Acknowledgements Thanks to INB (Industrias Nucleares do Brazil) for the supply of the samples.

Table 1. Chemical characterization of the effluent.

Parameters U Mn Ca Mg Al Zn Fe FSO42pH

Concentration (mg L-1) 6.8 107.5 104.9 7.6 164.2 17.7 <0.01 99.0 1349 2.97

Concentration after pH adjustment (mg L-1) <0.3 89.5 428 7.4 28.5 4.0 <0.01 38.0 1335 5.64

CONAMA 357 (mg L-1) 1.0 5.0 15.0 10.0 6 to 9

* Parameters expressed in mg L-1, except pH; - Permissible level not defined by Brazilian law.

References BAMFORTH, S.M.; MANNING, D.A.C.; SINGLETON, I.; YOUNGER, P.L.; JOHNSON, K.L. Appl. Geochem. 21, 1274-1287, 2006. ROBINSON-LORA, M.A.; BRENNAN, R.A. Chem. Eng. J., 162, 565-572, 2010.

SICUPIRA, D.C., SILVA, T.T., LEÃO, V.A., MANSUR, M.B. Braz. J. Chem. Eng., in press. CONAMA - Conselho Nacional do Meio Ambiente, n. 357: http://www.mma.gov.br/port /conama/index. cfm (2005).

LADEIRA, A.C.Q.; GONÇALVES, C.R. J. Hazard. Mat., 148, 499-504, 2007.

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publications

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MAJUSTE, D.; CIMINELLI, V.S.T.; OSSEO-ASARE, K.; DANTAS, M.S.S. Hydrometallurgy, vol. 113-114, p. 167-176, 2012.

CHAGAS, L.H.; FARIAS, S.B.P.; LEITÃO, A.A.; CHIARO, S.S.X.; SPEZIALI, N.L.; MUSSEL, W.N.; ABREU, H.A.; DINIZ, R., Química Nova, vol. 35 (6), p. 1112-1117, 2012. CHIBA, W.A.C.; PASSERINI, M.B.; BAIO, J.A.F.; TORRES, J.; TUNDISI, J.G. Braz. J. Biol, vol. 71, n. 4, p. 833-834, 2011.

MANSUR, M.B. REM. Revista Escola de Minas, vol. 64, p. 51-55, 2011. MANTUANO, D.P.; ESPINOSA, D.C.R.; WOLFF, E.; MANSUR, M.B.; Schwabe, W.K. Revista Brasileira de Ciências Ambientais, vol. 21, p. 1-13, 2011. MATSCHULLAT, J.; HOFLE, S.; SILVA, J.; MELLO, J.; MELO, G.; PLESSOW, A.; REIMANN, C. Geochemistry, vol. 12, p. 197-209, 2012.

PUBLICATIONS |

MELLO, N.A.S.T.; MAIA-BARBOSA, P.M.; SANTOS, A.M. Oecologia Australis, vol. 15 (3), p. 559-575, 2011. MELO, R.F.; DIAS, L.E.; MELLO, J.W.V.; OLIVEIRA, J.A. Revista Brasileira de Ciência do Solo, vol. 34, p. 985-992, 2010. MENINI, L.; PEREIRA, M.C.; FERREIRA, ANDRÉ C.; FABRIS, J.D.; GUSEVSKAYA, E.V. Applied Catalysis. A, vol. 392, p. 151-157, 2011. MOZETO, A.A.; MONTINI, M.; BRAZ, S.A.; MARTINS, F. G.; SOARES, A.; NASCIMENTO, M.L.R.; BARBOSA, F.A.R.; FADINI, P.S.; FARIA, B.M. Journal of Environmental Science and Engineering, v. A 1, p. 598-610, 2012. NASCIMENTO, C.K.; PEREIRA, M.C.; CAVALCANTE, L.C.D.; LANA, A. M.; MURAD, E.; BRAGA, J.P.; FABRIS, J.D. Hyperfine Interactions, vol. 203, p. 25-31, 2011. NOGUEIRA, F.G.E. ; LOPES, J.H.; SILVA, A.C.; LAGO, ROCHEL M.; FABRIS, J.D.; OLIVEIRA, L.C.A. Applied Clay Science, vol. 51, p. 385-389, 2011. OLIVEIRA, C.; LIMA, G.F.; ABREU, H.A.; DUARTE, H.A. Journal of physical chemistry C, vol. 116, p. 6357-6366, 2012. OLIVEIRA, C.; DUARTE, H.A. Appl. Surf. Sci, vol. 257(4), p. 1319-1324, 2010. OLIVEIRA, D.M.; MUSSEL, W.N.; DUARTE, L.P.; SILVA, G.D.F.; DUARTE, H.A.; GOMES, E.C.L. Quimica Nova, vol. 35 (10), 1916-1921, 2012. OT TONI, F.P.; LE Z AMA , A .Q.; TRIQUES, M.L.; FR AGOSO -MOUR A , E. N.; LUCAS, C.C.T.; BARBOSA, F.A.R. Vertebrate Zoology, v. 61, p. 137-145, 2011. PAIVA, D.N.B.; MATOS, J.M.G.; SILVA, J.C.J.; CIMINELLI, V.S.T. Revista Analytica, vol. 57, p. 68-71, 2012. PANTUZZO, F.L.; CIMINELLI, V.S.T. Water Research, vol. 44 (19), p. 5631-5640, 2010. PANZERA, T.H.; STRECKER K.; OLIVEIRA, L.G.; VASCONCELOS, W.L.; SCHIAVON, M.A. Materials Research, vol. 13, p. 535-540, 2011. PAUL A , J.F.R.; FROES -SILVA , ROBERTA E.S.; CIMINELLI, V.S.T. Microchemical Journal, vol. 104, p. 12-16, 2012. PAYE, H. S.; MELLO, J.W.V.; MELO, S.B. Revista Brasileira de Ciência do Solo, vol. 36, p. 1031-1042, 2012. P A Y E , H . S . ; M E L L O , J . W .V. ; A B R A H Ã O , W.A.P.; FERNANDES FILHO, E.I.; DIAS, L.C.P.; CASTRO, M.L.O.; MELO, S.B.; FRANÇA, M.M. Revista Brasileira de Ciência do Solo, vol. 34, p. 2041-2051, 2010. PEREIRA, M.C.; CAVALCANTE, L.C.D.; MAGALHÃES, F.; FABRIS, J.D.; STUCKI, J.W.; OLIVEIRA, L.C.A.; MURAD, E. Chemical Engineering Journal (1996), vol. 166, p. 962-969, 2011.

96 | ANNUAL ACTIVITY REPORT 2011-2012 — INCT-ACQUA

PEREIRA, M.C.; GARCIA, E.M.; SILVA, C.; ADILSON; LORENÇON, E.; ARDISSON, J.D.; MURAD, E.; FABRIS, J.D.; MATENCIO, T.; RAMALHO, T.C.; ROCHA, M.V.J. Journal of Materials Chemistry, vol. 21, p. 10280-10282, 2011. RIBEIRO, A.A.; LIMA, D.Q.; DUARTE, H.A.; MURAD, E.; PEREIRA, M.C.; SUITA, M.T.F.; Ardisson, J.D.; Fabris, J.D. Hyperfine Interactions, vol. 199, p. 1-4, 2011. RIBEIRO, A.A.; LIMA, D.Q.; DUARTE, HÉLIO A.; MURAD, ENVER; PEREIRA, MÁRCIO C.; SUITA, MARCOS T. D. F.; Ardissom, José D.; Fabris, J.D. Hyperfine Interactions, vol. 203 (1-3), p. 47-50, 2011. RODRIGUES, G.S.; CUNHA, I.S.; SILVA, G.G.; NORONHA, A.L.O.; ABREU, H.A.; DUARTE, H.A. IJQC, vol. 111, 1395-1402, 2011. SANT’ANNA, E.M.E.; SCHETTINO, M.; MENÉNDEZ, R.M.; GUIMARÃES, A.S.; MAIA-BARBOSA, P.M. Acta Limnologica Brasiliensia, vol. 22 (1), p. 102-10, 2010. SANTOS, E.A.; LADEIRA, A.C.Q. Tecnológica (UNISC), Vol.15, p. 22 - 29, 2011. SANTOS, E.A.; L ADEIRA, A.C.Q. Environmental Science & Technology, vol. 45, p. 3591-3597, 2011. SCHUCKNECHT, A.; MATSCHULLAT, J.; CARITAT, P.; SILVA, J.; MELO, G.; PLE OW, A.; MELLO, J.W.V. Science of the Total Environment, vol. 438, p. 342-356, 2012. SILVA, G.C.; CIMINELLI, V.S.T.; FERREIRA A.M.; ALMEIDA F.S.; PISSOLATI N.C. A facile synthesis of Mn3O4/ Fe3O4 super paramagnetic nanocomposites by chemical precipitation: Characterization and application in dye degradation. Materials Research Bulletin, 2013 (in press). SILVA, A.C.; CEPERA, R.M.; PEREIRA, M.C.; LIMA, D.Q.; FABRIS, J.D.; OLIVEIRA, L.C.A. Applied Catalysis. B, Environmental, vol. 107, p. 237-244, 2011. SILVA, G.C.; ALMEIDA F.S.; GUIMARÃES, A.M.F.; CIMINELLI, V.S.T. Materials Research, vol. 15 (3): 403-408, 2012. SILVA , G.C.; ALMEIDA , F.S.; DANTAS, M.S.S.; CIMINELLI, V.S.T. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, vol. 100, p. 161-165, 2013. SILVA, J.; MELLO, J.W.V.; GASPARON, M.; CIMINELLI, V.S.T.; ABRAHÃO, W.A.P. Water Air Soil Pollut, vol. 223, p. 5707-57-17, 2012. SILVA, J.; MELLO, J.W.V.; GASPARON, M.; ABRAHÃO, W.A.P. Water, Air and Soil Pollution (Dordrecht. Online), vol. 223, p. 6, 2012. SILVA, L.L.O.; VASCONCELOS, D.C.L.; NUNES, E.H.M.; CALDEIRA, L.; COSTA, V.C.; MUSSE, A.P.; HATIMONDI, S.A.; Nascimento, J.F.; Grava, W.; Vasconcelos, W.L. Ceramics International, vol. 38, p. 1943-1949, 2012. SOUZA, C.M.B.; MANSUR, M.B. Brazilian Journal of Chemical Engineering, vol. 28, p. 425-432, 2011. SOUZA, L.R.; LADEIRA, A.C.Q. Journal of Waste Management, vol. 2013, p. 1-7, 2013.

Book Chapters ALMEIDA, K.; MATSCHULLAT, J.; MELLO, J.W.V.; MENEZES, I.; VIOL A, Z. Physical aspects of the Iron Quadrangle. In: Jochen Bundschuh, Prosun Bhattacharya. (Org.) Arsenic: natural and anthropogenic. 3ed.The Netherlands: CRC Press/ Balkema, vol. 4, p. 81-90, 2011. BICUDO, C.E.M.; TUNDISI, J.G.; SCHEUENSTUHL, M.C. Ciência, Tecnologia, Inovação e Recursos Hídricos: Oportunidades para o futuro. 179-197 pp. In: Águas do Brasil: analises estratégica. 221 pp. São Paulo, Instituto de Botânica, 2010. BICUDO, C.E.M.; TUNDISI, J.G.; SCHEUENSTUHL, M.C. Síntese. 219-222 pp. In: Águas do Brasil: análise estratégica. 221 pp. São Paulo, Instituto de Botânica, 2010. DESCHAMPS, E.; MELLO, J.W.V.; MATSCHULLAT, J. Soils and sediments. In: Jochen Bundschuh, Prosun Bhattacharya. (Org.). Arsenic: natural and anthropogenic. 3ed.The Netherlands: CRC Press/ Balkema, vol. 4, p. 127-139, 2011. DUA RTE, H. A .; LOURENÇO, M.P.; HEINE, T.; GUIMARAES, L. Clay Mineral nanotubes: Stability, Structure and Properties. In: Alessio Innocenti; Norlida Kamarulzaman. (Org.). Stoichiometry and Materials Science - When numbers matter. 2 ed.: InTech, vol. 2, Chapter 1, p. 1-23, 2012. LIT TER, M.; CA RRER A , A .L.P.; CIRELLI, A .F.; INGALLINELL A, A.M.; FERNÁNDEZ, A.M.S.; NICOLLI, H.B.; PONCE, L.P.C.; LARROSA, N.A.M.; FARÍAS, S.S.; CIMINELLI, V.S.T. El problema del arsenic en el Mercosur. Un abordaje integrado y multidisciplinar y en la investigación y desarrollo para contribuir a su resolución. In: “Tecnologias para o Desenvolvimento Sustentável”, Brasília: Edições UNESCO, 2011 (Edição 2011 do Prêmio MERCOSUL de Ciência e Tecnologia). p. 85-110. NASCIMENTO, A.M.A. Use of the rRNA operon and genomic repetitive sequences for the identification of bacteria. In: Frans J. de Bruijn. (Org.) Handbook of Molecular Microbial Ecology I: Metagenomics and Complementary Approaches: Wiley-Blackwell, p. 29-40, 2011. OMETTO, J.P.; CIMBLERIS, A.C.P.; SANTOS, M.A.; ROSA, L.P.; ABE, D.S., TUNDISI; J.G., STECH, J.L.; BARROS, N.; ROLAND, F. Carbon dynamic and emissions in Brazilian hydropower reservoirs. In: Energy Resources Development. Nova Science Publishers, pp.155-188, 2011. ROCHA, S.D.F.; RIBEIRO, M.V.; VIANA, P.R.M.; MANSUR, M.B. Bone char: an alternative for the removal of diverse organic and inorganic compounds from industrial wastewaters. In: Amit Bhatnagar (Org.) Application of Adsorbents for Water Pollution Control. 1st ed.: Sharjah, Bentham Science Publishers, vol. Único, p. 502-522, 2012.

SANTOS, F.R.; LACERDA, D.R.; REDONDO, R.A.F.; NASCIMENTO, A.M.A.; CHARTONE-SOUZ A, E.; BORBA E.L.; RIBEIRO R.A.; LOVATO, M.B. DIVERSIDADE GENÉTICA. IN: DRUMOND G.M.; MARINS C.S.; GRECO M.B.; VIEIRA F. (Org.). Biot Minas: diagnóstico do conhecimento sobre a diversidade no Estado de Minas Gerais subsídio ao Programa Biota Minas. Belo Horizonte: Fundação Biodiversitas. Belo Horizonte: Fundação Biodiversitas, 2010, p. 389-410. TUNDISI J.G. & SCHEMENTSUL M.C. Waste Policy in Brazil. In: Jimenez B. & Tundisi. J. G. (Editors). Water Policy in the América. IANAS Publication.

Books ABE, D.; ROLAND, F.; ROLAND, F.; SANTOS, M.A.; STECH, J.L.; SIGAGIS GALLI, C.V.; SANTOS, E.O.; DAMAZIO, J.M. Diretrizes para análises quantitativas de emissões líquidas de gases de efeito estufa em reservatórios,1 ed., Rio de Janeiro: MME, vol. 2, 95p., 2012. BERE, T.; TUNDISI, J.G. Diatom communities as indicators of ecological infairment in rivers: conservation and water quality management. Lambert Academic Publications, 228pp. 2012. BICUDO, C. E. M.; TUNDISI, J. G.; SCHEUENSTUHL, M.C. Águas do Brasil: análises estratégicas. Instituto de Botânica, São Paulo, 221 pp. 2010. CISNEROS, B.J., TUNDISI, J.G. (Coordinators). Diagnostico Del Agua em las Americas. IANAS, Foro Consultivo y Tecnologico, AC 447 pp. 2012. JORGENSEN, S. E., TUNDISI, J.G.; MATSUMURATUNDISI, T. Handbook of inland aquatic ecosystem management. Taylor & Francis, CRC Press. 422pp. 2012. SIDAGIS GALLI, C.; ABE, D.; SANTOS, E.O.; ROLAND, F.; STECH, J.L.; SANTOS, M.A. Estado da Arte em Ciclo de Carbono em reservatórios, 2 ed., Rio de Janeiro: MME, vol. 2, 237, p. 2012. TUNDISI, J. G.; MATSUMURA-TUNDISI, T. Limnology. Taylor & Francis, CRC Press, 864 pp, 2012. TUNDISI, J. G.; MATSUMURA-TUNDISI, T. Recursos Hídricos no Século XXI. Editora Oficina de Textos, 328 pp., 2011.

Patents Process for recovery of cyanide and copper from effluents from the extraction of gold-copper ores and electroplating. Deposited in 10/05/2011, protocol number: 014110002916. Virginia S. T. Ciminelli, Douglas Moreira de Oliveira, Adélia Moreira de Oliveira, Geraldo Luiz da Silva. Process for the recovery of cyanide and copper 07/22/2008, PI 0802832-0 – Virginia S. T. Ciminelli, Clauson de Souza, Geraldo Luiz da Silva.

PUBLICATIONS |

contacts INCT-ACQUA MANAGEMENT COMMITTEE Virginia Sampaio T. Ciminelli – UFMG, Director José Galizia Tundisi – IIEGA-SP, Vice-Director Francisco Antônio Rodrigues Barbosa – UFMG, Vice-Director Ângela de Mello Ferreira – CEFET-MG Ana Claudia Queiroz Ladeira – CNEN/ CDTN Jaime Wilson Vargas de Mello – UFV Hélio Anderson Duarte – UFMG

EXECUTIVE OFFICE Dr. Claudia L. Caldeira, Assistant Manager claudia@demet.ufmg.br

Christina Salvador, Secretary inct.acqua@demet.ufmg.br

Gabriela Meira Maia, Public Information Officer inctacqua@gmail.com

CESUP (ALTO PARAOPEBA) OFFICE Dra. Maria de Lourdes Almeida, Project Manager cesup@altoparaopeba.mg.gov.br

FUNDEP – FUNDAÇÃO DE DESENVOLVIMENTO DA PESQUISA Luis Felinto Xavier Nascimento, Project Analyst luisnascimento@fundep.ufmg.br

UFMG – UNIVERSIDADE FEDERAL DE MINAS GERAIS Department of Metallurgical and Materials Engineering Berenice Mendonça González gonzalez@demet.ufmg.br

Marcelo Borges Mansur marcelo.mansur@demet.ufmg.br

Virginia S.T. Ciminelli ciminelli@demet.ufmg.br

Wander Luiz Vasconcelos wlv@demet.ufmg.br

Chemistry Department Cláudia Carvalhinho Windmoeller claucw@netuno.lcc.ufmg.br

Hélio Anderson Duarte duarteh@ufmg.br

Heitor Avelino de Abreu heitorabreu@ufmg.br

Rodnei Augusti augusti@ufmg.br

Department of General Biology Andréa Maria A. Nascimento amaral@ufmg.br

Arnola Cecília Rietzler rietzler@icb.ufmg.br

Edmar Chartone de Souza echartone@yahoo.com.br

Francisco Antônio R. Barbosa barbosa@icb.ufmg.br

Paulina Maria Maia Barbosa maia@icb.ufmg.br

Pharmacy School Sérgia Maria Starling Magalhães sergiams@farmacia.ufmg.br

School of Architecture Flávio de Lemos Carsalade

flavio.carsalade@terra.com.br

School of Fine Arts Francisco Carlos de Carvalho Marinho flavio.carsalade@terra.com.br

Luiz Antonio Cruz Souza

luiz.ac.souza@gmail.com

Wallace Lages

wallace.lages@gmail.com

IIEGA – ASSOCIAÇÃO INSTITUTO INTERNACIONAL DE ECOLOGIA Corina Verónica Sidagis Galli csg.iie@iie.com.br

Donato Seiji Abe

donatoabe@iie.com.br

José Eduardo Matsumura Tundisi edu@iie.com.br

José Galizia Tundisi

CEFET/MG – CENTRO FEDERAL DE EDUCAÇÃO TECNOLÓGICA DE MINAS GERAIS Andréa Rodrigues Marques Guimarães andrearmg@gmail.com

Ângela de Mello Ferreira angelamello@des.cefetmg.br

Sidney Nicodemos da Silva sidney@des.cefetmg.br

UFCe – UNIVERSIDADE FEDERAL DO CEARÁ Igor Frota de Vasconcelos ifvasco@ufc.br

UFJF – UNIVERSIDADE FEDERAL DE JUIZ DE FORA Júlio César José da Silva silvajc@yahoo.com.br

Otavio Eurico de Aquino Branco otavio.branco@ufjf.edu.br

UFSJ – UNIVERSIDADE FEDERAL DE SÃO JOÃO DEL REI Luciana Guimarães lucianaguimaraes@ufsj.edu.br

UFVJM – UNIVERSIDADE FEDERAL DOS VALES DO JEQUITINHONHA E MUCURI José Domingos Fabris jdfabris@gmail.com

SECTES/MG – SECRETARIA DE ESTADO DE CIÊNCIA, TECNOLOGIA E ENSINO SUPERIOR Maria Margarida Marques mmmarques@icb.ufmg.br

Polo de Excelência Mineral e Metalúrgico

jgt.iie@iie.com.br

Renato Ciminelli

Takako Matsumura Tundisi

presidencia@geoparkquadrilatero.org

takako@iie.com.br

Valéria Silva Pizzo

valeria@iie.com.br

CNEN/CDTN – COMISSÃO NACIONAL DE ENERGIA NUCLEAR/ CENTRO DE DESENVOLVIMENTO DE TECNOLOGIA NUCLEAR Ana Cláudia Queiroz Ladeira ana.ladeira@cdtn.br

Carlos Antônio de Morais cmorais@cdtn.br

Paulo César Horta Rodrigues pchr@cdtn.br

Rubens Martins Moreira rubens@cdtn.br

UFV – UNIVERSIDADE FEDERAL DE VIÇOSA Igor Rodrigues de Assis igor.assis@ufv.br

Jaime Wilson V. de Mello jwvmello@ufv.br

INTERNATIONAL COLLABORATION Dina L. Lopez - Ohio University, USA lopezd@ohio.edu

Harmut Gliemann - Karlsruhe Institute of Technology, Germany hartmut.gliemann@kit.edu

Jack Ng - University of Queensland, Australia j.ng@uq.edu.au

K. Osseo-Asare - The Pennsylvania State University, USA ako1@psu.edu

Marta Litter - CNEA, Argentina marta.litter@gmail.com

Massimo Gasparon - University of Queensland, Australia m.gasparon@uq.edu.au

Michael Nicol - Murdoch University, Australia m.nicol@murdoch.edu.au

Peter Georg Weidler - Karlsruhe Institute of Technology, Germany peter.weidler@kit.edu

Luiz Eduardo Dias

Susan Glasauer - University of Guelph, Canada

ledias@ufv.br

glasauer@uoguelph.ca

Walter Antônio Pereira Abrahão

Thomas Heine - Jacobs University, Germany

wabrahao@ufv.br

t.heine@jacobs-university.de CONTACTS |

From left to right: Wander Luiz Vasconcelos, Virginia S.T. Ciminelli, Berenice Mendonça González and Marcelo Borges Mansur; Hélio Anderson Duarte; Francisco A.R. Barbosa; Renato Ciminelli; Jaime Wilson Vargas de Mello; Fernando Souza Soares, Valéria Teixeira da Silva, Fernando de Paula Blanco, Cileise Priscila Pereira de Lima, José Galizia Tundisi, Pedro Gatti Júnior, Takako Matsumura Tundisi, Donato Seiji Abe, Carlos Rogério Lopes Faria, Leandro Contri Campanelli, Corina Veronica Sidagis Galli and Ricardo Milanetti Degani.

From left to right: Paulina Maria Maia Barbosa; Heitor Avelino de Abreu; Ana Cláudia Queiroz Ladeira, Peter Fleming, Paulo César Horta Rodrigues, Carlos Alberto de Carvalho Filho and Carlos Antônio de Morais; Angela de Mello Ferreira, Andréa Rodrigues Marques Guimarães and Paulo Renato Perdigão Paiva; Claudia L. Caldeira; Christina Salvador.

Headquarters

Universidade Federal de Minas Gerais – UFMG Escola de Engenharia – Bloco II Depto. de Engenharia Metalúrgica e de Materiais Av. Antonio Carlos, 6627 – 31270-901 Belo Horizonte – MG, Brazil

Telephone

+55 (31) 3409-1825 / 1769

E-mail

inct.acqua@demet.ufmg.br

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